PhysChem 2013 Pre Conference Workshop 3 December Conference 4-6 December Hobart Waterfront www.physchem2013.com.au Conference Handbook Decoding the Nanoworld

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Welcome 4 Conference General Information 5-6 Pre-Conference Workshop 7-9 Conference Program 10-17 Social Program 18-19 Abstracts and Biographies 21-75 Poster Presentations 76-162 Sponsorship & Exhibition 163-169

Conference Organising Committee

Dr Tak W. Kee Dr Adam Trevitt University of Adelaide University of Wollongong

Prof Evan Bieske Prof Jeff Reimers University of Melbourne University of Sydney

Dr David Huang Dr Duncan Wild University of Adelaide University of Western Australia

Dr Angus Gray-Weale University of Melbourne

Conference Managers

Leishman Associates 113 Harrington Street, Hobart TAS 7000 Phone: 03 6234 7844 Fax: 03 6234 5958 Mobile: 0408 625 033 Email: [email protected] Web: www.leishman-associates.com.au

3 www.physchem2013.com.au Welcome

Welcome to the Royal Australian Chemical Institute conference, PhysChem 2013, and to beautiful Hobart.

This meeting promises to be an exciting event. The conference organising committee would particularly like to welcome our international plenary speakers to Australia, and thank them for their contributions throughout the meeting. They headline an exciting program, with an outstanding line-up of speakers and poster presenters. We would like to thank you all for contributing to this line-up, and hope that you enjoy the program ahead.

A warm welcome and thank you are also extended to our sponsors and exhibitors. We deeply appreciate your support of this meeting and your commitment to the RACI Physical Chemistry Division and the physical chemistry community.

If you can, spend a day or two to enjoy Hobart, and beautiful Tasmania (not during conference session times!). There are many things that make Tasmania special. Outstanding wilderness areas, beautiful beaches, dramatic seascapes, a rich history, weird art, and some of the best beer and wine available in Australia to complement fine food served in a relaxed atmosphere.

It’s our pleasure to welcome you to RACI PhysChem 2013, on behalf of the conference organising committee. We look forward to your participation.

Dr Tak W. Kee Prof Evan Bieske School of Chemistry School of Chemistry & Physics University of Melbourne University of Adelaide

Co-Chairs RACI PhysChem 2013 4 www.physchem2013.com.au Conference General Information

Registration Desk Conference Name Badges

The Registration Desk will be located All delegates, speakers, sponsors in the main foyer of the Tasmanian and exhibitors will be provided with School of Art, Hunter Street and will a name badge, which must be worn be open at the following times: at all times within the conference venue, as it is required for access to all the conference sessions and social Registration Desk opening functions. Times:

Wednesday 4 December 2013: Conference Proceedings 8:00am – 6:00pm The conference abstracts will be Thursday 5 December 2013: available on the RACI PhysChem 8:00am – 6:00pm website following the conclusion of the conference. To obtain copies of Friday 6 December 2013: presentations during the conference, 8:00am – 6:30pm please contact the speakers directly.

Accommodation Dress

If you have any queries relating to Dress throughout the day and social your accommodation booking first events is smart casual. speak to the staff at your hotel or alternatively Leishman Associates Internet staff at the Registration Desk. There will be wireless internet Your credit card details were supplied available in the conference venue to the hotel you have selected, as for the duration of the conference. security for your booking. If you You will be supplied with an internet have arrived 24 hours later than code upon registration. your indicated arrival day you may find that you have been charged a fee. You will be responsible for all Mobile Phones room and incidental charges on check out and may be asked for an As a courtesy to other delegates, impression of your credit card for please ensure that all mobile security against these charges. This is phones are turned off or in a silent standard policy in many hotels. mode during all sessions and social functions.

5 www.physchem2013.com.au Photographs, Videos, Disclaimer Recording of Sessions The 2013 RACI PHYSCHEM conference Delegates are not permitted to use reserves the right to amend or alter any type of camera or recording any advertised details relating to device at any of the sessions unless dates, program and speakers if written permission has been obtained necessary, without notice, as a from the relevant speaker. result of circumstances beyond their control. All attempts have been made to keep any changes to an Speakers absolute minimum.

Speakers will be asked to bring their presentations with them on a CD or USB stick, then load their presentations onto the computer in the theatre. This must be done AT LEAST by the break prior to your presenting time – this may mean the day before your presentation. There will be dedicated speakers assistants to provide help uploading your file. All speakers are responsible for ensuring their presentation is uploaded and ready for their session. Please see the staff at the Registration Desk for further information.

Special Diets

All catering venues have been advised of any special diet preferences you have indicated on your registration form. Please identify yourself to venue staff as they come to serve you and they will be pleased to provide you with all pre-ordered food. For day catering, there may be a specific area where special food is brought out, please check with catering or conference staff.

6 www.physchem2013.com.au Pre - Conference Computational Chemistry Workshop

Date: Tuesday 3 December 2013 Location: Room 327, Chemistry Building, UTAS, Sandy Bay Campus Workshop Fee: $80.00

Please note that attendees need to participants less familiar with make their own way to and from the computational methods how to pre-conference workshop. apply these methods to standard problems and an advanced stream The one-day workshop will be comprising master classes by guest held the day before the start of lecturers focussing on particular the conference. It will provide an computational problems or methods. introduction to computational Participants can choose which chemistry methods, including sessions from the two streams they molecular orbital methods, semi- attend empirical theories, density functional theory (DFT), molecular dynamics The pre-conference workshop is an and Monte Carlo simulations, integral optional delegate activity. You must equation theories of liquids, and pre-purchase a ticket to attend this computational spectroscopy. workshop. Please note that spaces are limited. The workshop will consist of two parallel streams: an introductory stream aimed at teaching

7 www.physchem2013.com.au Pre - Conference Workshop Tuesday 3 December 2013

Optional Pre - Conference Computational Chemistry Workshop University of Tasmania, Sandy Bay Campus

9:00 am – Welcome and Introduction 9:20 am C2 Lecture Theatre, Room 329

9:20 am – Session 1: Quantum chemistry 10:00 am A/Prof Meredith Jordan, The University of Sydney C2 Lecture Theatre, Room 329

10:00 am – Morning Refreshments 10:20 am Chemistry Staff Room, Room 208

Stream 1 - Introduction to Stream 2 - Master Classes Computational Chemistry

Computer Lab, Room 327 C2 Lecture Theatre, Room 329

10:20 am – 11:10 am Explicit correlation: 10:20 am – accelerating basis set 12:00 pm Session 1 (continued) convergence Dr Jo Lane, The University of Waikato

11:10 am – 12:00 pm Dynamics of open quantum systems A/Prof Kenneth Brown, Georgia Institute of Technology

12:00 pm – Lunch 12:50 pm Chemistry Staff Room, Room 208

1:00 pm – 1:50 pm Molecular dynamics simulation of non-equilibrium 1:00 pm – Session 2: Classical systems Prof Debra Bernhardt, 2:40 pm molecular simulations The University of Queensland Dr David Huang, The University of Adelaide 1:50 pm – 2:40 pm Quantum mechanics for condensed phases Prof Julian Gale, Curtin University

8 www.physchem2013.com.au 2:40 pm – Afternoon Refreshments 3:00 pm Chemistry Staff Room, Room 208

3:00 pm – 3:50 pm Computational electronic and vibrational spectroscopy A/Prof Tim Schmidt, The University of Sydney

3:00 pm – Session 3: An introduction 3:50 pm – 4:40 pm 5:30pm to the statistical Sampling rare but important mechanics of solvation trajectories and interfaces Prof Phillip Geissler, University of Dr Angus Gray-Weale, California, Berkeley The University of Melbourne 4:40 pm – 5:30 pm Exploring conformational space and conformational averaging Prof Michelle Coote, Australian National University

5:30 pm – Closing Remarks 5:50 pm C2 Lecture Theatre, Room 329

9 www.physchem2013.com.au PhysChem 2013 Pre Conference Workshop 3 December Conference 4-6 December Hobart Waterfront www.physchem2013.com.au

10 www.physchem2013.com.au Wednesday 4 December 2013 The Tasmanian School of Art, Hunter Street

8:00 am Registration Desk Opens The Main Foyer

8:45 am Official Conference Opening Remarks The Dechaineux Theatre

Plenary Session The Dechaineux Theatre

9:00 am How complicated can crystal growth really be? Prof Julian Gale, Curtin University

Contributed Papers

9:45 am Do Classical Electrostatics Determine the Magnetic Anisotropy of Low-Symmetry Dysprosium Complexes? Dr Alessandro Soncini, The University of Melbourne

10:00 am Classical density functional theory of solvation, interfaces, and surfactant assembly Dr Angus Gray-Weale, The University of Melbourne

10:15 am Beryllium Chemistry the Safe Way – A Quantum Chemical Investigation Dr David Wilson, La Trobe University

10:30 am Morning Refreshments The Main Foyer

Keynote Session The Dechaineux Theatre

11:0 0 am High-Coherence Electron and Ion Bunches from Laser-Cooled Atoms A/Prof Rob Scholten, The University of Melbourne

Contributed Papers

11:3 0 am Can Molecular Dynamics Reveal the Active Conformation of Insulin? Dr Naomi Haworth, Monash University

11:4 5 am How do cryoprotective agents damage cell membranes at high concentration? A molecular dynamics simulation study Prof Ricardo Mancera, Curtin University

11 www.physchem2013.com.au Keynote Session The Dechaineux Theatre

12:00 pm pH Switching Radical Stability and Orbital Conversion Prof Michelle Coote, Australian National University

Contributed Papers

12:30 pm Density functional theory calculations of organo-modified silicene Dr Michelle Spencer, RMIT University

12:45 pm Molecular Meccano and Neurodegeneration: The Computational Challenges Dr Cyril Curtain, Mental Health Research Institute of Victoria

1:00 pm Lunch The Main Foyer

1:55 pm Welcome Address from the Major Sponsor

The Dechaineux Theatre Dr Shane Huntington, Director, The Innovation Group Pty Ltd

Plenary Session The Dechaineux Theatre

2:00 pm Line ‘em all up: assembly at complex liquid interfaces Prof Geraldine Richmond, University of Oregon, USA

Contributed Papers

2:45 pm Conjugated Polymer Films Imaged at High Spatial and Temporal Resolution A/Prof Trevor Smith, The University of Melbourne

3:00 pm Molecular Approaches to Next Generation Photovoltaics A/Prof Timothy Schmidt, The University of Sydney

3:15 pm Controlling Resonance Energy Transfer between Dyes on a Co-Sensitised Metal-Oxide Surface Dr Viktoras Dryza, The University of Melbourne

3:30 pm Afternoon Refreshments The Main Foyer

12 www.physchem2013.com.au Keynote Session The Dechaineux Theatre

4:00 pm Remote but not disinterested: Measuring the effect of charge on radical stabilisation in distonic radical anions Prof Stephen Blanksby, University of Wollongong

Contributed Papers

4:30 pm NMR Chemical Shift in molecules with a (quasi)- degenerate Ground State Dr Willem Van Den Heuvel, The University of Melbourne

4:45 pm The THz/Far-IR Beamline at the Australian Synchrotron Dr Courtney Ennis, Synchrotron Light Source Australia

5:00 pm Electronic energies, molecular structures and frequencies by systematic molecular fragmentation Prof Michael Collins, Australian National University

5:15 pm Super-resolution localization microscopy of transfected cells, starved cells and mitochondria Dr Toby Bell, Monash University

5:30 pm Session Close

6:00 pm- Welcome Reception and Poster Session 1 The Main Foyer 9:00 pm The Tasmanian School of Art, Hunter Street

Thursday 5 December 2013 The Tasmanian School of Art, Hunter Street

8:00 am Registration Desk Open The Main Foyer

Plenary Session The Dechaineux Theatre

9.0 0 am Ultrafast Studies of Single Metal and Semiconductor Nanostructures Prof Greg Hartland, University of Notre Dame, USA

9:45 am Student Award Winner The Photon of Persuasion: Influencing Branching Fractions in the Photodissociation of H2CO Mitchell Quinn, The University of Sydney

Contributed Papers

13 www.physchem2013.com.au 10.00 am 'Hot' Photo-induced Electron Transfer Prof Ken Ghiggino, The University of Melbourne

10.15 am Modelling Nano-Scale Structure and Energy Transfer in Conjugated Polymers Dr David Huang, The University of Adelaide

10:30 am Morning Refreshments The Main Foyer

Keynote Session The Dechaineux Theatre

11. 0 0 am Shearing nanoconfined fluids Prof Debra Bernhardt, The University of Queensland

Contributed Papers

11:3 0 am Adiabatic energy surfaces: the interplay between electronic coupling and electron-vibrational coupling that controls chemical reactivity, spectroscopy, and the development of entanglement Prof Noel Hush, The University of Sydney

11:4 5 am Spin-system crossing points in reaction mechanisms Prof Brian Yates, University of Tasmania

Keynote Session The Dechaineux Theatre

12.00 pm Are bond critical points really critical for hydrogen bonding? Dr Joseph Lane, The University of Waikato, New Zealand

12:30 pm Lunch The Main Foyer

The remainder of the afternoon is free for independent exploration of Hobart! What to see and do? Visit the website for more information www.physchem2013.com.au Want to visit the world famous MONA? Ferry departs at 1:15 pm. Pre-book your tickets @ www.mona.net.au

6:00 pm – Poster Session 2 The Main Foyer 9:00 pm The Tasmanian School of Art, Hunter Street

14 www.physchem2013.com.au Friday 6 December 2013 The Tasmanian School of Art, Hunter Street

8:00 am Registration Desk Open The Main Foyer

Plenary Session The Dechaineux Theatre

9:00 am Probing Actinide Bonding using Multiphoton Excitation and Photoelectron Spectroscopy Prof Michael Heaven, Emory University, USA

Contributed Papers

9:45 am Assignment of the Q-Bands of the Chlorophylls: Coherence Loss via Qx-Qy Mixing Prof Jeffrey Reimers, The University of Sydney

10:00 am Quantum enhancement of steady-state light harvesting in sunlight Dr Ivan Kassal, The University Of Queensland

10:15 am Morning Refreshments The Main Foyer

Keynote Session The Dechaineux Theatre

10:45 am Harnessing the Power of the Sun – Self-Assembled Porphyrin-fullerene Complexes as Functional Components A/Prof Cather Simpson, The University of Auckland, New Zealand

Contributed Papers

11:15 am Reactivity of Gallium Nano-clusters Dr David Henry, Murdoch University

11:3 0 am Metal Clusters on Oxide Surfaces for Catalysis A/Prof Gunther Andersson, Flinders University

Keynote Session The Dechaineux Theatre

11:4 5 am Photodissociation of small aromatic species in the gas-phase and liquid-phase microdroplets Dr Adam Trevitt, University of Wollongong

Contributed Papers

15 www.physchem2013.com.au 12:15 pm Ligand-mediated control of the surface plasmon resonance in metal nanoparticles generated by laser ablation Prof Mark Buntine, Curtin University

12:30 pm Roaming, roaming everywhere Prof Scott Kable, The University of Sydney

12:45 pm Lunch The Main Foyer

Plenary Session The Dechaineux Theatre

1:45 pm Probing molecular ions with laser-cooled atomic ions A/Prof Kenneth Brown, Georgia Institute of Technology, USA

Contributed Papers

2:30 pm Resonance and Photoisomerization in Fluorescent Protein Chromophores: Reversible Photobleaching Rate and Proximity to the Cyanine Limit Dr Seth Olsen, The University of Queensland

2:45 pm Reactive Simulations of Carbonates in Water Dr Paolo Raiteri, Curtin University

3:00 pm Effective and ineffective transition metal catalysis in reversible hydrogen storage Dr Terry Frankcombe, Australian National University

3:15 pm Afternoon Refreshments The Main Foyer

Keynote Session The Dechaineux Theatre

3:45 pm Ultrafast Probes of Free Charge Photogeneration in Organic Photovoltaics Dr Justin Hodgkiss, Victoria University of Wellington, New Zealand

Contributed Papers

4:15 pm Aerosol icing on the cake: IR spectroscopy of nanoscale particles Dr Evan Robertson, La Trobe University

4:30 pm Helium Nanodroplet Isolation Spectroscopy of Hydridotrioxygen and of its Complexes with Dioxygen Dr Paul Raston, The University of Adelaide

16 www.physchem2013.com.au 4:45 pm Can dianions make strong gas phase bases? Dr Berwyck Poad, University of Wollongong

5:00 pm Rotational spectroscopy of PANH and cyano substituted PAH species Prof Donald McNaughton, Monash University

5:15 pm Understanding electronic structures of molecules from gamma-ray spectroscopy Dr Feng Wang, Swinburne University of Technology

Keynote Session The Dechaineux Theatre

5:30 pm Ab initio molecular dynamics of molecules in strong laser fields Prof H. Bernhard Schlegel, Wayne State University, USA

6:00 pm Conference Closing Remarks

7:00 pm – Conference Dinner 10:00 pm The Mill on Morrison, Hobart

17 www.physchem2013.com.au Conference Social Program

Welcome Reception & Poster Session 2 Poster Session 1

Proudly sponsored by Innovation Group / Venue: University of Tasmania, NewSpec Fine Arts Building, Hobart Date: Thursday 5 December 2013 Time: 6:00pm – 9:00pm Dress: Smart Dress

Inclusive function Additional tickets are available Venue: University of Tasmania, for $80.00 Fine Arts Building, Hobart Date: Wednesday 4 December 2013 Join us for the second poster session Time: 6:00pm – 9:00pm for RACI PhysChem 2013. Dress: Smart Dress Authors will be available to speak about their posters during this session. Inclusive function Light food and beverages will be Additional tickets are available served. for $80.00

Join us for the official welcome reception and poster session. Authors will be available to speak about their posters during this session and it is a great opportunity to network with new colleagues and to catch up with friends. The evening will included canapés and beverages in a relaxed environment.

18 www.physchem2013.com.au Conference Dinner

Proudly sponsored by Innovation Group / NewSpec

Venue: The Mill on Morrison, 11 Morrison Street, Hobart Date: Friday 6 December 2013 Time: 7:00pm – 10:00pm Dress: Smart Dress

Inclusive Event. Additional tickets are available for $130.00

Come and join us on the last night of the conference program for another chance to network and meet with colleagues, whilst enjoying a great night of food and wine at The Mill on Morrison.

Transport is not provided for the conference dinner. Instead a walking map will be provided upon registration at the conference venue.

19 www.physchem2013.com.au A bright future, defined by a rich past.

The University of Tasmania was founded over 123 years ago, making it one of Australia’s oldest universities. Today we’re recognised as an international leader, ranked in the top 2% of universities in the world.* Academic Ranking of World Universities 2013 Universities World of Ranking Academic It’s that merging of rich heritage with strength of character * that guarantees our greatest achievements are still to come.

utas.edu.au | 13UTAS USRM11222rj CRICOS Code: Provider 00586B Abstracts & Biographies Wednesday 4 Authors Raffaella Demichelis ¹, Paolo Raiteri ², December 2013 Julian D. Gale ³, Adam F. Wallace , Jim De Yoreo 5, Andrew G. Stack 6, Matthias Kellermeier 7, Denis Gebauer 8

1. NRI, Department of Chemistry, Curtin Plenary Session University, PO Box U1987, Perth, WA 6845, [email protected]

9:00am-9:45am 2. NRI, Department of Chemistry, Curtin University, PO Box U1987, Perth, WA 6845, [email protected] How complicated can crystal growth really be? 3. NRI, Department of Chemistry, Curtin University, PO Box U1987, Perth, WA 6845, [email protected] Prof Julian Gale Curtin University 4. The Molecular Foundry/Earth Sciences, Lawrence Berkeley National Laboratory, Biography Berkeley, CA 94720, [email protected]

Julian Gale was awarded his 5. Physical Sciences Division, Pacific first degree from University of Northwest National Laboratory, Richland, Oxford where he also obtained WA 99352, USA, [email protected] his DPhil in the Dept. of Chemical 6. Chemical Sciences Division, Oak Crystallography. After a post-doctoral Ridge National Laboratory, PO Box 2008, position at the Royal Institution of Tennessee 37831, USA, [email protected] Great Britain he moved to Imperial College London to take up a 7. Dept. of Physical Chemistry, University of Royal Society University Research Konstanz, Konstanz, Germany, Matthias. [email protected] Fellowship in the Department of Chemistry, where he subsequently 8. Dept. of Physical Chemistry, University became Reader in Theoretical and of Konstanz, Konstanz, Germany, Computational Chemistry. In 2003, [email protected] Julian moved to Curtin University as one of two inaugural Premier’s Abstract Research Fellows awarded by the Crystal growth is ubiquitous, both in Government of Western Australia the laboratory and the natural world. where he also served as acting As a result there have been theories director of the Nanochemistry to explain crystallisation that go back Research Institute and as a member over a century, and have evolved of the Premier’s Science and along with our atomic view of matter. Innovation Council. Currently he Even after all this time, this field of is an ARC Professorial Fellow in research is still presenting challenges the Department of Chemistry with to our understanding. In the case of Curtin’s Resources and Chemistry calcium carbonate (CaCO3), one Precinct. of the most widespread minerals at the Earth’s surface, there has been considerable debate regarding the nucleation and growth mechanisms.

22 www.physchem2013.com.au Firstly, it was recognised that in 9:45am-10:00am many natural systems crystalline polymorphs form via an amorphous Do Classical Electrostatics precursor phase, rather than by direct nucleation. Secondly, and Determine the Magnetic most recently, the existence of stable Anisotropy of Low-Symmetry pre-nucleation clusters was proposed Dysprosium Complexes? by Gebauer et al [1], in apparent contravention of classical nucleation Authors theory. Dr Alessandro Soncini 1 , Nicholas Chilton2, Prof David Collison 2, Prof Eric McInnes 2, In this presentation computer Prof Richard Winpenny 2, simulation, based on molecular dynamics with a thermodynamically 1. The University of Melbourne 2. The University of Manchester accurate force field, will be used to probe the early and late stages of growth of calcium carbonate Biography from aqueous solution. In particular, Dr Soncini is a theoretical chemist, the question of why the initial ion with interest in the theory of association is stable, and what electronic structure, magnetic and the form of these prenucleation conduction properties of molecules clusters is, will be examined [2]. It and molecule-based materials. will be shown that through careful Before coming to the University of determination of the free energy Melbourne in 2011 as a lecturer, he landscape [3] it is possible to gain held positions in Italy, in the UK, in new insights into the complex Belgium and Norway. emergence of crystalline materials via multiple amorphous and liquid- Abstract like precursor states [4], as well as how Understanding the anisotropic they grow subsequent to nucleation. electronic structure of lanthanide complexes is important in areas [1] D. Gebauer et al, Science, 322, 1819 as diverse as magnetic resonance (2008) imaging, luminescent cell labelling [2] R. Demichelis et al, Nature Commun., and quantum computing. We present 2, 590 (2011) an intuitive theoretical model based on a classical electrostatic picture, [3] A.G. Stack et al, J. Am. Chem. Soc., capable of predicting the magnetic 134, 11 (2012) anisotropy of dysprosium(III) complexes, even in low symmetry. The [4] A.F. Wallace et al, (in press) strategy relies only on knowing the X-ray structure of the complex and Key Words the well-established observation that, Crystal growth; simulation; calcium in the absence of high symmetry, carbonate; molecular dynamics; the ground state of dysprosium(III) nucleation is a doublet quantized along the anisotropy axis with an angular momentum quantum number mJ = ±15/2. The magnetic anisotropy axis of fourteen low symmetry monometallic 23 www.physchem2013.com.au dysprosium(III) complexes computed We focus on the longest range via high-level ab initio calculations correlations between solvent are very well reproduced by our molecules, and find a dispersion force electrostatic model. Furthermore, we arising from correlations between show that the magnetic anisotropy is the thermally rotating dipole equally well predicted in a selection moments. This force, which attracts of low symmetry polymetallic each pair of molecules, has usually complexes. been assumed negligible, and so it seems in a mean-field treatment that regards other waters near the two in question as a dielectric continuum. 10:00am – 10:15am Using exact results for the correlations between permanent moments, we Classical density functional show that this attraction is stronger than expected, and that it has a theory of solvation, interfaces, surprising temperature dependence and surfactant assembly that coincides with the observed temperature dependence of the Authors hydrophobic effect. Our treatment Cameron Ritchie1, Maoyuan Liu1, is consistent with the observed Quinn Besford1, Angus Gray-Weale1 cold denaturation of proteins, estimates well the vaporisation 1. The University of Melbourne entropies of many polar fluids, and

Abstract captures hydrophobes’ signature, temperature-dependent, interfacial, Classical density functional theory solvation, and protein-unfolding (CDFT) provides a method for thermodynamics. the systematic calculation of fluid structure at interfaces and We discuss the pH-dependence around solutes, and of related the of the surface tension of water thermodynamic properties. It suffers as an example of an interfacial from few or none of the problems measurement that may be used to of accuracy and consistency that test theories of interfacial structure come with mean-field or continuum and thermodynamics, and use this methods such as ‘polarisable example to point out the failings continuum’ or Poisson-Boltzmann of methods based on the Poisson- methods. The difficulty of obtaining Boltzmann method. solutions to the CDFT equations has limited its use to crude models. Here Finally, we use an exact result for the we discuss the application of these strength of dispersion forces between methods to polar and associating fluids of thermally rotating dipole liquids, especially water, without the moments to predict which solvents need for ad hoc assumptions. We support the assembly of surfactants look at solvation structure, interfacial into micelles. This prediction performs structure, and the tendency of as well as the best known empirical surfactants to assemble in various prediction method, but is derived solvents. from exact results on the free energy of a polar liquid.

24 www.physchem2013.com.au Key Words be presented for the Be analogue classical density functional theory, of the important Mg(I)–Mg(I) dimer dispersion forces, interfaces, surfactant supported by the β-diketiminate assembly ligand. The study of “molecule allotropes” state has recently become a topic of importance in p-block chemistry [2-3]. In this case, 10:15am – 10:30am our results demonstrate that the Be(0) complexes are far more stable than Beryllium Chemistry the Safe the analogous Mg(0) complexes, highlighting the opportunities Way – A Quantum Chemical afforded in Be chemistry, despite Investigation the challenges presented by the toxicity of Be compounds. Advanced Authors bonding analysis, including energy Dr David Wilson, Dr Jason Dutton decomposition analysis (EDA) sheds La Trobe University light on the bonding and electronic structure of these novel species. Biography David Wilson obtained his PhD in Be has also been reported to 2003 from the University of Newcastle, undergo ring insertion into NHCs, a Australia. He then took up a 2-year phenomenon that has also been postdoctoral fellowship with Prof. observed for B and Si species. Results Trygve Helgaker at the University of will be presented for a study of the Oslo, Norway, working on the Dalton mechanism of ring formation, in program and studying magnetic which similarities between then three and electric properties. In 2005 he systems will be outlined. gained an appointment at La Trobe University, Australia. His current research is centred around applying quantum chemistry to systems with novel bonding environments.

Abstract As part of a study of the binding and electronic structure of low- oxidation state elements (“molecular allotropes”) stabilised by donor ligands such as N-heterocyclic carbenes (NHCs), we have investigated the properties of Be and Be2 in a 0 oxidation state [1]. Standard undergraduate teaching of Mos suggests that neutral Be2 should have a bond order of zero and thus be unstable. Here we report a means to stabilise Be2 to make a viable molecule. Results will also 25 www.physchem2013.com.au Keynote Session cooled atoms offer a new approach to generating high brightness and 11:00am – 11:30am high coherence charged particle beams for applications including ultrafast electron diffractive imaging High-Coherence Electron and of dynamic processes at the Ion Bunches from Laser-Cooled nanoscale. The effective brightness Atoms of electron sources has been limited by non-linear divergence A/Prof Rob Scholten caused by repulsive interactions The University of Melbourne between the electrons, known as the Coulomb explosion. It has been Biography shown that electron bunches with ellipsoidal shape and uniform density Robert Scholten is a Professor distribution have linear internal of Physics at The University of Coulomb fields [1], allowing reversal Melbourne, where he leads the of the Coulomb explosion using Ultracold Plasma high-brightness conventional optics. A cold atom electron source Project of the ARC electron source can create bunches Centre of Excellence in Coherent shaped in three dimensions and in X-ray Science. His research career principle achieve the transverse began with studying electron spatial coherence and brightness collisions from laser-excited atoms, needed for picosecond diffractive where laser polarisation was used imaging with nanometre resolution. to control the quantum state of the target atoms. His interest in We have demonstrated [2] laser-atom interactions formed the arbitrary shaping of the cold atom basis of later research, for example cloud (Fig. 1), and hence of the using atom-optics techniques for extracted electron bunches, and nanofabrication as a Fulbright used the shaping capability to Postdoctoral Research Fellow at NIST allow detailed measurement of the in the USA. He has also developed spatial coherence properties of the novel approaches to optical imaging cold electron source [3]. We also of cold atoms, is currently working on show remarkable ion bunch shape quantum sensing using colour centres formation and evolution, with direct in diamond, and has created a high- visualisation made possible by the tech start-up company (MOGLabs) very low (milliKelvin) temperature of based on lasers and laser electronics. the ions. Using a counter-intuitive two-step femtosecond excitation Authors and nanosecond ionisation scheme, RE Scholten, BM Sparkes, D Murphy, DJ we have generated electron Thompson, R Speirs, J Torrance, R Taylor bunches with durations of a few ARC Centre of Excellence for Coherent hundred picoseconds [4]. Diffraction X-ray Science, School of Physics, The experiments of simple crystalline University of Melbourne, Australia. materials are currently in progress, Abstract to demonstrate application of the high coherence of the novel source. Cold atom electron and ion sources Future development of the cold based on photoionisation of laser 26 www.physchem2013.com.au atom electron source will increase [2] A. J. McCulloch, D. V. Sheludko, M. the bunch charge and charge Junker, S. C. Bell, S. D. Saliba, K. A. Nugent, density, demonstrate reversal of and R. E. Scholten, Nature Physics 7, 785 Coulomb explosion and picosecond (2 011). pulse durations, and ultimately, [3] S. D. Saliba, C. T. Putkunz, D. V. ultrafast coherent electron diffractive Sheludko, A. J. McCulloch, K. A. Nugent, imaging. and R. E. Scholten, Optics Express 20 (4) 3967 – 3974 (2012).

[4] A. J. McCulloch, D. V. Sheludko, M. Junker and R. E. Scholten, High coherence picosecond electron bunches from cold atoms, Nature Communications 4 1692 (2013).

11:30am – 11:45am

Can Molecular Dynamics Reveal the Active Figure 1: (a) A bunch of electrons Conformation (left) has of Insulin? been produced with a complex spatial distribution, and because of the low electron temperature (10 K) the bunch has retained its shape after Authors propagating 24cm. (b) Images of propagated ion bunches (right) show two adjacent expanding 1 2 ion bunches; excitation laser beam Dr Naomi intensity Haworth profile , Briony for an array of miniature Forbes ion, -­‐A/Profbunches, and far Andrea Robinson 1. right, complex pattern formed by Coulomb effects between the bunches during propagation. 1. Monash University, Figure 1: (a) A bunch of electrons (left) has 2. Flinders University been produced with a complex spatial Figure 1: (a) A bunch of electrons distribution, (left) and has because been of the produced low with a complex spatial distribution, and because of the low electron electrontemperature temperature (10 K) (10 K) the the bunch bunch has retained its shape after Biography propagating 24cm. (b) Images of has retained propagated its shape ion after bunches propagating (right) show two adjacent expanding Dr Haworth completed her BSc(Hons) ion bunches; excitation laser beam 24cm. intensity (b) Images profile of propagated for an array of miniature ion-­‐bunches, ion and far in Chemistry at Quantum Physics at bunches (right) show two adjacent right, complex pattern formed by Coulomb effects between the bunches during propagation. the University of Melbourne followed expanding ion bunches; excitation laser beam intensity profile for an array of by a PhD in Theoretical Chemistry at miniature ion-bunches, and far right, the University of Sydney under the complex pattern formed by Coulomb supervision of Dr George Bacskay. effects between the bunches during She has worked as a postdoctoral propagation. researcher in the groups of Professor Leo Radom at the University of References Sydney and Professor Tim Clark in [1] O. J. Luiten, S. B. van der Geer, M. J. Erlangen Germany (as a Humboldt de Loos, F. B. Kiewiet, and M. J. van der Fellow) as well as holding research Wiel, Phys. Rev.Lett. 93, 094802 (2004); B. positions with the Victor Chang J. Claessens, S. B. van der Geer, G. Taban, Cardiac Research Institute, Deakin E. J. D Vredenbregt, and O. J. Luiten, Phys. University and Monash University. Rev. Lett. 95, 164801 (2005).

27 www.physchem2013.com.au Abstract We have used molecular dynamic Insulin is an essential hormone simulations to probe the effects of which is responsible for controlling replacing the A6-A11 disulfide of the metabolism of carbohydrates wild-type human insulin with both and fats. Failure of the body to E and Z dicarba linkages. Starting adequately produce and/or respond geometries were taken from four to insulin results in diabetes mellitus, independent insulin crystal structures, one of the major health challenges each having different disulfide facing Australia in the 21st century. bond conformations. All simulations Current insulin analogues used in of both wild-type insulin and of diabetes treatment have significant the active dicarba insulin isomer drawbacks. They require patients converge to a single conformation to undergo regular injections, can (the “positive” conformation). In be unstable unless stored and contrast, simulations for the inactive transported with care and have isomer converge to one of two the potential to cause undesirable structures, neither of which aligns well side effects. However, the targeted with that of the active isomer. While development of alternative these two “negative” conformations insulin therapies requires a good occupy neighbouring regions understanding of the behaviour of of conformational space to the insulin in the body, in particular how it “positive” conformation, important binds to the insulin receptor (IR) and components of the insulin structure signals the initiation of the glucose which are known to be essential metabolism pathway. While steady for IR binding and activation have progress is being made in this field, been displaced. These include the the “active” conformation of insulin N-terminus of the A chain (GlyA1) and required for IR binding and the details the sidechain of residue GluA4. It is of the insulin-IR interactions are still hoped that these results will provide unknown. valuable insights in the search for the elusive “active” conformation of Insulin consists of two polypeptide insulin. chains (A and B) linked by two disulfide bonds (A7-B7 and A20-B19). A third disulfide connects residues 6 and 11 of the A chain. Recently this intrachain disulfide has become a target for modifications seeking to improve insulin stability. A particularly interesting variant involves replacement of the disulfide with a carbon-carbon double bond linkage (a “dicarba” bridge). Two possible isomers can be formed, involving either E or Z stereochemistry around the double bond. Crucially, one of these isomers has almost identical biological activity to wild-type insulin, while the other is inactive.

28 www.physchem2013.com.au 11:45am – 12:00pm polyols (such as glycerol, ethylene glycol and propylene glycol) being How do cryoprotective agents frequently used in mixtures referred to as vitrification solutions. These agents damage cell membranes have good cryoprotective abilities at high concentration? but can be toxic to cells at high A molecular dynamics concentration. We have conducted simulation study a large number of molecular dynamics simulations to investigate Authors the mechanism of damage of these Prof Ricardo Mancera, Dr Zak Hughes, agents on model cell membranes Chris Malajczuk composed of different types of Curtin University phospholipid bilayers and sterols.

Biography DMSO induces the expansion and thining of both DPPC and Ricardo Mancera is Professor of DOPC bilayers (1). Above a critical Biomolecular Modelling at Curtin concentration, pores in the University in Perth. He obtained his membranes form spontaneously and, PhD at the University of Cambridge if the concentration increases further, and then held research and the bilayer structure is completely academic positions in Cambridge destroyed (1). DOPC bilayers are and then at Curtin University, where more resistant to these deleterious he is currently the Head of the effects as the free energy barrier Biomolecular Modelling Group. for the diffusion of DMSO is higher Ricardo has diverse research interests due to the longer acyl chains (1). in protein structure, dynamics and Addition of sterols stabilises DOPC interactions; biomolecular hydration; bilayers, reducing the area per lipid, cell membranes; aqueous solutions; increasing bilayer thickness and ligand-protein interactions; drug the order of the phospholipid acyl discovery and molecular modelling chains (2). Sterols make membranes methods. more resistant to the deleterious effects of DMSO and prevent the Abstract formation of pores (2). Polyols Cryopreservation allows the storage induce a similar lateral expansion of biological tissues at liquid nitrogen and lipid disordering on DPPC, temperatures through the use of DOPC and DOPC/sterol bilayers cryoprotective agents (CPAs) that (3, 4). Propylene glycol and DMSO promote the formation of the vitrified damage membranes the most state of water and minimise the (including the formation of pores) deleterious formation of ice crystals. due to their higher hydrophobicity In these conditions all physical, (3, 4). The increase in concentration chemical and biological processes of polyols induces the formation of are arrested and cells and tissues a cross-linked CPA layer across the can be preserved for decades. surface of the bilayers, especially Penetrating CPAs can cross cell with glycerol due to its higher ability membranes, dehydrate cells and to cross-link lipid headgroups and promote the vitrification of water order membranes (3). Sterols diminish upon rapid cooling, with DMSO and the deleterious effects of polyols 29 www.physchem2013.com.au in a similar fashion to DMSO, in this as an ARC postdoctoral fellow with case by reducing hydrogen-bonding Professor Leo Radom. She established between the bilayer and the CPAs her own research group in 2004 and as well as headgroup cross-linking is currently an ARC Future Fellow. (4). Mixtures of these agents induce She has published extensively in the bilayer thinning to a much lower fields of polymer chemistry, radical degree than DMSO at the same chemistry and computational overall concentration, explaining quantum chemistry, and received the synergistic effects and reduced many awards including the 2001 toxicity of vitrification solutions. IUPAC prize for young scientists, the RACI Cornforth medal (2000), Rennie References medal (2006) and David Sangster [1] Hughes, Mark & Mancera, J Phys Chem Polymer Science and Technology B, 2 012, 116, 11911. Achievement Award (2010), and the Le Fevre Memorial Prize of the [2] Hughes & Mancera, Soft Matter, 2013, Australian Academy of Science 9, 2920. (2010).

[3] Malajczuk, Hughes & Mancera, BBA - Authors Biomembranes, 2013, 1828, 2041. Ganna Gryn’ova, and Michelle L. Coote [4] Hughes, Malajczuk & Mancera, J Phys Chem B, 2013, 117, 3362. Abstract The electronic configuration of an atom or a molecule is normally defined according to the aufbau Keynote Session principle: ‘a maximum of two electrons are put into orbitals in the 12:00pm – 12:30pm order of increasing orbital energy’. However, a limited number of recent publications have reported non- pH Switching Radical Stability aufbau occupation of molecular and Orbital Conversion orbitals in radicals, where the molecular orbital accommodating Prof Michelle Coote the unpaired electron (the singly- Australian National University occupied molecular orbital, or SOMO) is no longer energetically Biography the highest occupied molecular Professor Michelle Coote is a orbital (HOMO). Recently, we have graduate of the University of New discovered a brand new class South Wales, where she completed of fully organic SOMO-HOMO a B.Sc. (Hons) in industrial chemistry converted compounds, and the (1995), followed by a Ph.D. in first such species capable of being polymer chemistry (2000). Following manipulated by pH. Using quantum- postdoctoral work at the University of chemical calculations, validated Durham, UK, she joined the Research by gas-phase thermochemistry School of Chemistry, Australian experiments carried out in the National University in 2001, initially group of Steve Blanksby, we have shown that distonic radical anions 30 www.physchem2013.com.au comprising a stabilized radical (such ¹(a) Gryn’ova, G., Marshall, D.L., Blanksby, as an aminoxyl, peroxyl or aminyl S.J., & Coote, M.L. Nature Chem., 5, 474- functionality) that is not conjugated 481 (2013) (b) Gryn’ova, G., & Coote, M.L. (or hyperconjugated) with a remote submitted. negatively charged functional group (such as a carboxylate, phosphate, sulphate, alkoxide anion) undergo SOMO-HOMO conversion. When the negatively charged group is protonated the Aufbau orbital configuration is restored (see Fig. 1). Intriguingly, we also found that SOMO-HOMO orbital conversion is associated with a dramatic and unprecedented effect on the stability of the radical, significantly weakening the bonds it forms with hydrogen and with carbon-centred radicals. This long-range substituent Figure 1 effect on radical stability, which is Figure 1. Deprotonation of carboxy- TEMPO results in both SOMO-HOMO likewise switched off by protonation, orbital . conversion Deprotonation and an increase of carboxy-­‐TEMPO in persists even in radicals that have no results radical in stability both by-­‐ SOMO HOMO nearly orbital 4 orders of conversion polar resonance contributors, and and magnitude an increase at room temperature in radical stability by nearly 4 even remains when the negatively orders of magnitude at room temperature charged groups are deleted altogether and replaced by point charges (i.e. electric fields). This talk 12:30pm – 12:45pm will outline the scope, origin and potential applications of the unusual stability and electronic structures of Density functional theory these distonic radical anions. calculations of organo- modified silicene Key Words SOMO-HOMO conversion, radical Authors stability, polar effects, distonic radical Dr Michelle Spencer ¹, Michael Bassett ², anions, quantum chemistry Dr Tetsuya Morishita ³, Dr Hideyuki Nakano

References 1. RMIT University, 2. La Trobe University, ¹IUPAC. Compendium of Chemical 3. Nanosystem Research Institute, Terminology, 2nd ed. (the “Gold Book”). 4. Toyota Central

¹(a) Sugawara, T., Komatsu, H. & Suzuki, K. Biography Chem. Soc. Rev. 40, 3105-3118 (2011). (b) Kusamoto, T., Kume, S. & Nishihara, H. J. Dr Spencer is a Senior Lecturer Am. Chem. Soc. 130, 13844-13845 (2008). in Chemistry at RMIT University, (c) Kobayashi, Y., Yoshioka, M., Saigo, K., and leader of the Computational Hashizume, D. & Ogura, T. J. Am. Chem. Materials Chemistry group. Soc. 131, 9995-10002 (2009).

31 www.physchem2013.com.au After completing her Honours and properties. As the interaction energy PhD at La Trobe University she between the sheets is very weak held research fellow and senior we show that including vdWs forces research fellow positions at RMIT in the DFT calculations is essential University, followed by an academic to model the interaction between appointment at La Trobe University. organo-modified silicene nanosheets, She also currently holds a Visiting giving a marked improvement Scientist position at CSIRO and an in the predicted equilibrium Honorary Fellow appointment at separation distance determined from the University of Melbourne. Her experimental measurements. As the research focuses on using density modified nanosheets are brought functional theory and ab initio closer together, the phenyl groups molecular dynamics calculations to on the bottom of one nanosheet can investigate a variety of materials and fit in between the phenyl groups on nanomaterials for applications as the top of the adjacent nanosheet, gas sensors, batteries and electronic allowing some interaction between devices. the aromatic rings. The band gap can also be modified by compressing Abstract the nanosheets together while retaining a small attraction between Two-dimensional (2D) nanomaterials them. The unique properties of are currently one of the most this nanomaterial could be useful intensely studied areas of research. for building stacked structures for 2D nanosheets of silicon are one such optoelectronic applications. example and have been successfully grown via a variety of methods. A References single layer Si nanosheet, called silicene, has been synthesised with [1] H. Nakano, T. Mitsuoka, M. Harada, K. Horibuchi, H. Nozaki, N. Takahashi, different surface functionalisations, T. Nonaka, Y, Seno, H. Nakamura, including the phenyl-modified Angewandte Chemie International Edition silicene that has been grown 45 (2006) 6303-6. and studied by our group [1,2]. This material has phenyl groups [2] Y. Sugiyama, H. Okamoto, T. Mitsuoka, attached to silicene above and T. Morikawa, K. Nakanishi, T. Ohta, H. below the nanosheet with the under- Nakano, J. Am. Chem. Soc. 132 (2010) coordinated Si atoms terminated 594 6 -7. by H atoms. Using density functional [3] M.J.S. Spencer, M. Morishita, M. theory (DFT) calculations, we Mikami, I.K. Snook , Y. Sugiyama, H. showed that this new nanomaterial Nakano, Phys. Chem. Chem. Phys. 13 is semiconducting, with a direct (2011) 15418-22. band gap [3]. From the experimental synthesis, the nanosheets are likely to be stacked on top of each other at a separation distance of ~10Å [2], however, no details are known about their stacking geometry and adhesive force, or how the separation distance between the sheets could modify the structural or electronic

32 www.physchem2013.com.au 12:45pm – 1:00pm in a number of diseases. Selection of the initial β-structures from an Molecular Meccano and apparently random pool is poorly understood. Because of side chain Neurodegeneration: The steric interference, some structures Computational Challenges are frustrated and the pool may not be truly random. Post-translationally Authors modified residues provide an Cyril C. Curtain1, Timothy Ryan1, Kevin additional complication. This is J. Barnham1, Colin L. Masters1, Roberto 1 2 2 particularly relevant to the study of Cappai , Robert B. Knott , Agata Rekas the key proteins in the amyloids of 1. The University of Melbourne, neurodegeneration, the Aβ peptide 2. Australian Nuclear Science and of Alzheimer’s and α-synuclein of Technology Organisation (ANSTO) Parkinson’s diseases. Here, redox processes in the brain can lead Biography to changes such as nitration of tyrosine residues or oxidation of Cyril Curtain, D.Sc., FRACI is a methionine residues. Oxidation of biophysical chemist. He is currently its four methionine residues renders a Senior Fellow of the Florey Institute α-synuclein incapable of forming of Neuroscience and Mental Health pre-amyloid fibrils. Using small angle at the University of Melbourne where X-ray scattering at the Australian he studies protein misfolding in Synchrotron we have shown neurodegeneration employing small that oxidation of the methionine angle X-ray scattering techniques residues of α-synuclein eliminates at the Australian Synchrotron and the extended structures from the small angle neutron scattering at ensemble derived from the pool the Bragg Institute, Lucas Heights. of structures1. Understanding how His interest in protein misfolding in a small change in four residues in neurodegeneration goes back 50 140 can give such a result may lead years when he was associated with Dr to insights into how fibril formation Carleton Gajdusek in his pioneering might be inhibited by targeting study of Kuru in Papua New Guinea. these extended structures in IDPs. This poses substantial computational Abstract challenges with a range of solutions, A significant fraction of every pro none of which are completely teome is occupied by biologically satisfactory. Here, we shall describe active proteins that do not form some approaches to solving the unique three-dimensional structures. α-synuclein ensemble problem that Many of these intrinsically disordered might have general applicability to proteins (IDPs) have essential other pathological IDPs. biological functions and possess extensive structural plasticity. This Reference may enable IDPs to perform different 1.Pham CLL, Kirby N, Wood K, Ryan et al. functions in different environments. Guanidine Hydrochloride Denaturation The disadvantage is that many of Dopamine Induced α-Synuclein IDPs can also form cross-spine Oligomers: A Small Angle X-ray Scattering β-structures, creating amyloids and/ Study. Proteins 2013 Jun 4. doi: 10.1002/ or cytotoxic oligomers occurring prot.24332. [Epub ahead of print] 33 www.physchem2013.com.au Plenary Session conditions were traditionally used. The assembly of thin films at liquid/ solid and liquid/liquid interfaces 2:00pm – 2:45pm fall into this category as well the multitude of unique nanostructured materials that assemble in solvents Line ‘em all up: assembly at and at surfaces. We have also complex liquid interfaces begun to see advances in moving the synthesis and assembly of these Prof Geraldine Richmond materials to more environmentally University of Oregon, USA benign solvents, such as in aqueous solutions, where complex interactions Biography between the water solvent and the Geraldine (Geri) Richmond is the largely hydrophobic material can Presidential Chair and Professor play a controlling role. This increased of Chemistry at the University of complexity of the materials growth Oregon in Eugene, Oregon, USA. Her environment is usually accompanied research using laser spectroscopy by less predictability, often because and computational methods of our limited knowledge of the focusses on understanding the fundamental molecular interactions chemistry and physics that occurs that lead to the assembly and at complex interfaces that have stability of molecules at these relevance to important problems in interfaces. energy production, environmental remediation and atmospheric This presentation gives an chemistry. She is also active in overview of ongoing research in efforts to increase the number and my laboratory that is aimed at success of women in the sciences obtaining a molecular level picture around the world through the COACh of the adsorption and assembly organization which she founded in of surfactants, nanoparticles and 1997. Richmond is a member of the macromolecules from aqueous U.S. National Academy of Sciences solution to fluid surfaces. We and ,the American Academy of Arts. employ both experimental and computational methods to Abstract unravel the complex structural, Over the past decade we have reactive and bonding interactions witnessed many exciting advances present at these interfaces. These in the laboratory towards the fundamental studies have direct development of new materials, in relevance to many important areas the area of molecular architecture of technological interest including and nanoscience, as well as in the environmental remediation, development of new “bio-inspired” waste water treatment, green materials that seek to emulate chemistry, materials growth, surface materials that have evolved in nature. wetting and hydrophobicity, and Many of these new materials are macromolecular assembly. being made in more complex and reactive environments than in the past where vacuum or clean-room

34 www.physchem2013.com.au 2:45pm – 3:00pm in efficient and low-cost solar cells. The morphology of thin films of Conjugated Polymer Films these materials is highly dependent on the conditions under which Imaged at High Spatial and the film is cast. We have applied Temporal Resolution super-resolution optical imaging methods and time-resolved emission Authors imaging to study the morphology A/Prof. Trevor Smith 1,2, Dr. Xiaotao and photophysics of thin films of Hao 3, Dr. Clare Henderson 1,2, Ben 1,2 various bulk heterojunction materials Morrison including poly(3-hexylthiophene) 1. The University of Melbourne, (P3HT) blended with electron 2. ARC Centre of Excellence for Coherent acceptors including nanodiamond X-Ray Science (CXS), (ND) particles. 3. Shandong University, ND particles have been introduced Biography in order to form novel hybrid Trevor Smith co-heads the Ultrafast nanocomposites because of their and Microspectroscopy Laboratories facile surface functionalisation, in the School of Chemistry at the biocompatibility, etc.1 In these University of Melbourne. His present composites, the absorption of solar research interests include time- photons by the polymer generates resolved fluorescence studies excitons, which may dissociate at the and super-resolution fluorescence polymer-ND interface, transferring imaging techniques applied to a electrons to the ND and leaving wide range of systems including positive polarons on the polymer. polymers, biological and botanical However, the photoinduced charge samples. He also has strong research separation and recombination interests in evanescent wave-induced processes remain unclear in this fluorescence studies and ultrafast novel nanocomposite material. We laser spectroscopy. A particular have investigated photoexcited interest is the use of time-resolved physical processes in films of P3HT-ND and super-resolution fluorescence nanocomposite by steady state and microscopy techniques to study time resolved optical spectroscopy polymer films for organic photovoltaic and microscopy. Fluorescence devices. He is currently a member decay measurements show a of the Australian Research Council reduction in the emission decay time Centre of Excellence for Coherent of the hybrid film compared with the X-Ray Science (CXS) coupling super- P3HT film, which most likely results resolution optical imaging techniques from the charge separation between with coherent X-ray diffractive P3HT and ND. Time resolved images imaging. allow mapping the dynamics of the photoinduced charge transfer/ transport processes as a function Abstract of location in the films. Species with Conjugated polymer-based hybrid longer lifetime (~200ps) are uniformly nanocomposites have gained distributed in P3HT film, while regions worldwide attention in recent years exhibiting a shorter emission lifetime due to their potential application (~130ps) in the hybrid film may be 35 www.physchem2013.com.au attributed to the charge separation on the electronic spectroscopy of induced by the ND aggregates that highly unsaturated hydrocarbons of are evenly dispersed in the polymer astrophysical relevance. Tim returned matrix. Femtosecond transient to Australia in 2003 to work at the absorption measurements have also CSIRO (CTIP, Lindfield) on modelling of been performed on these films. Based the rubsico enzyme. He commenced on these experimental observations, as a lecturer in chemistry in April 2004 the photoinduced physical processes at The University of Sydney, and was and dynamics are analysed and appointed Associate Professor in 2011. discussed. This study indicates Tim is appointed as Professor at The that P3HT-ND bulk heterojunction University of New South Wales from composites have great potential in 2014. He is the recipient of the 2010 photovoltaic application. Coblentz Award.

Abstract The sun provides more energy to our 3:00pm – 3:15pm planet in one hour than our species requires in an entire year. However, Molecular Approaches to Next harvesting this energy directly as Generation Photovoltaics electricity using single-threshold solar cells is fundamentally limited to an Authors upper efficiency of about 33%. This is primarily due to two factors: the A/Prof Timothy Schmidt 1, Rowan inability to absorb sub-bandgap light, MacQueen 1, Dr Yuen Yap Cheng 1, Dr Tim Schulze 2, Dr Murad Tayebjee 3, Dr Andrew and the degradation of energy in Nattestad 4, Andrew Danos 1, Dr Angus excess of the band gap. Gray-Weale 5, Prof Maxwell Crossley 1, Prof Klaus Lips 2, Sub band gap absorption may be addressed by upconversion. 1. The University of Sydney, In our laboratory, we have been 2. Helmholtz Zentrum Berlin, investigating sensitized triplet-triplet 3. UNSW, annihilation as a means to upconvert 4. University of Wollongong, sub-bandgap photons. In this 5. The University of Melbourne scheme, sensitizer molecules absorb Biography low energy photons, and rapidly undergo intersystem crossing to a Tim Schmidt gained his BSc (Hons) metastable triplet state. This triplet from this university in 1998 winning energy is transferred to an emitter the University Medal in theoretical molecule, the triplet of which is chemistry. He then studied at about half the energy of the lowest Churchill College, Cambridge, singlet. Subsequent annihilation of gaining a PhD in chemistry from two emitter triplets brings about the University of Cambridge in one singlet excited emitter, which 2001 for work on the femtosecond fluoresces at an energy above that of dynamics of molecules in intense the initially absorbed photons. laser field under the supervision of Dr Gareth Roberts. Postoctoral work was performed in the group of Professor John Paul Maier in Basel 36 www.physchem2013.com.au model for the exciton dynamics in tetracene which touches on a range of phenomena including super- radiance, singlet fission and self- trapping.[5]

Overall, this talk will show the contribution to be made to the photovoltaic area by molecular FIG 1: Augmentation of solar cell quantum spectroscopists, and that the detailed efficiency with upconversion understanding and control of energy flow in molecular materials can be harnessed to bring about the solar Application of this photochemical cells of the future. upconversion process to amorphous silicon, polymer and dye-sensitized solar cells has resulted in measurable improvements to the sub-band gap photon-to-electron conversion efficiency.[1,2,3] However, the efficiencies are still low, with current augmentations in the 10 3 mA/ cm2 range – about two orders of magnitude below what is required. Work to improve the efficiency using nanostructures is ongoing, and the latest results will be presented.

The opposite process to triplet- FIG 2: Initial radiative dynamics of a triplet annihilation, singlet fission, tetracene thin film takes place in organic crystals. In this case, one photon gives rise to References multiple excitons which may be [1] Y. Y. Cheng, B. Fückel, R. W. individually harvested to boost MacQueen, T. Khoury, R. G. C. R. Clady, the current for photons exceeding T. F. Schulze, N. J. Ekins-Daukes, M. J. about twice the band gap. Our Crossley, B. Stannowski, K. Lips and T. W. theoretical investigations have shown Schmidt, Energy Environ. Sci., 2012,5, 6953- that maximum efficiency at room 6959 temperature relies on endothermic [2] A. Nattestad, Y. Cheng, R. W. singlet fission, with an optimized cell MacQueen, T. F. Schulze, F. W. Thompson, capable of 46%. [4] A. J. Mozer, B. Fückel, T. Khoury, M. J. Crossley, K. Lips, G. G. Wallace, T. W We have investigated singlet fission Schmidt, J. Phys. Chem. Letters, 2013, 4 in tetracene films, which display (12), 2073–2078 endothermic fission. By varying the temperature, and performing [3] T. F. Schulze, J. Czolk, Y. Cheng, B. Fückel, R. W. MacQueen, T. Khoury, M. J. spectroscopy across six orders of Crossley, B. Stannowski, K. Lips, U. Lemmer, magnitude in time-scale (100fs to A. Colsmann, and T. W. Schmidt, J. Phys. 100ns), we have arrived at a unified Chem. C, 2012 116 (43), 22794-22801 37 www.physchem2013.com.au [4] M. J. Y. Tayebjee, A. A. Gray-Weale, of the electrode with two dyes having and T. W. Schmidt, J. Phys. Chem. Lett., complementary absorption spectra 2012, 3 (19), 2749-2754 has been employed. However, resonance energy transfer (RET) [5] M. J. Y. Tayebjee, R. G. C. R. Clady and Timothy W. Schmidt, Phys. Chem. Chem. between the two dyes usually limits Phys., 2013, DOI: 10.1039/C3CP52609G the achievable increase in solar conversion efficiency.

In this presentation, we demonstrate 3:15pm – 3:30pm that RET between organic dyes on a co-sensitised metal-oxide surface can be virtually eliminated Controlling Resonance Energy by deliberately misaligning the Transfer between Dyes on a excitation transition dipole moments Co-Sensitised Metal-Oxide of the two dyes. This is achieved by Surface exploiting the different chemical groups on each dye used to bind to Authors the electrode and which govern the relative orientation of the two dyes on Dr Viktoras Dryza, Prof Evan Bieske the surface. This maximises the light- The University of Melbourne harvesting efficiency by insulating the excited state of the short- Biography wavelength absorbing dye against Viktoras Dryza received his PhD in RET, preserving its superior electron 2008 from the University of Adelaide, injection capacity. under the supervision of Gregory Metha. He then commenced The experiments are conducted postdoctoral studies at the University in the gas phase by laser probing of Melbourne, working with Evan charged dye-sensitised metal-oxide Bieske in the field of gas-phase nanoparticles suspended in an molecular ion spectroscopy. He is ion trap and recording their time- currently an Australian Renewable resolved fluorescence decay curves. Energy Agency postdoctoral fellow, The presence of RET is determined conducting research into the light- by observing a decrease in the harvesting properties of organic dye donor dye’s excited state lifetime sensitisers for solar cell technologies. upon addition of the acceptor dye. The acceptor dye molecule has a Abstract benzoic acid anchoring group, which Dye-sensitsed solar cells (DSSCs) causes the dye to sit perpendicular are excellent candidates as next- to the surface. Detrimental RET generation solar cells, as they interactions occur when the can be constructed from cheap, donor dye molecule possesses environmentally friendly materials. a cyanoacrylic acid anchoring Within a DSSC, dye sensitiser group, which causes the dye to molecules anchored to a metal- sit perpendicular to the surface, oxide electrode absorb photons whereas RET is eliminated when the and inject the promoted electrons donor dye molecule possesses a into the circuit. In order to engineer rhodanine acetic acid anchoring panchromatic DSSCs, co-sensitisation group, which causes the dye to lie 38 www.physchem2013.com.au parallel to the surface. This concept Abstract will help guide the rational design of Distonic radical anions are ionised efficient co-senstised DSSCs. molecules wherein the radical and anion cannot be formally localised on a common atom. Recent high- level electronic structure calculations Keynote Session have revealed that even remote negative charges in distonic radical 4:00pm – 4:30pm anions can afford significant stabilisation to the radical moiety. This effect is apparent where homolytic Remote but not disinterested: bond energies remote from an acidic Measuring the effect of charge functional group can be lower by on radical stabilisation in up to 35 kJ mol−1 in the conjugate- distonic radical anions base (i.e., anionic) form compared with those in the conjugate-acid (i.e., Prof Stephen Blanksby neutral). These findings demonstrate University of Wollongong that simple deprotonation of an acid moiety can flip a “pH-switch”, effectively activating remote bonds Biography – some up to 10 Å away – toward Stephen Blanksby holds a PhD (1999) homolysis. In an effort to observe in gas phase ion chemistry from the this surprising thermochemical University of Adelaide (with Prof J.H. phenomenon we measured the gas Bowie) and undertook postdoctoral phase acidity (GPA) of the aminoxyl research at the Technical University radical 4-carboxy-TEMPO (A) and its of Berlin (1999, with Prof H. Schwarz) closed-shell, aminoether analogue C and at the University of Colorado (see Figure) using the kinetic method (with Prof G.B. Ellison). Blanksby was on a tandem mass spectrometer. appointed to the School of Chemistry Consistent with theoretical at the University of Wollongong in predictions, these measurements 2002 and was promoted to Professor revealed an enhancement in acidity in 2012. His research interests are at of ca. 20 kJ mol−1 in the presence the interface between fundamental of the remote radical moiety (i.e., ion chemistry, spectroscopy and GPA[C] − GPA[A] = 20 kJ mol−1). analytical mass spectrometry. Analogous experiments conducted across a test set of reference acids Authors established a critical benchmarking David L. Marshall1,3, Stephen J. Blanksby1,3, tool for the calculations with a 2,3 2,3 Ganna Gryn’ova , Michelle L. Coote mean absolute deviation of just 1.7 kJ mol−1. Moreover, by a simple 1. School of Chemistry, University of Wollongong, NSW, AUSTRALIA thermochemical cycle the measured difference in gas phase acidity 2. Research School of Chemistry, (ΔGPA = GPA[C] − GPA[A]) is shown Australian National University, ACT, to be equivalent to the difference in AUSTRALIA NO-CH3 bond dissociation energies 3. ARC Centre of Excellence for Free (ΔGPA = ΔBDE = BDE[C] − BDE[D] ), Radical Chemistry and Biotechnology thus providing direct experimental

39 www.physchem2013.com.au evidence for this remote radical Abstract stabilization is distonic radical ions [1]. The chemical shift and other parameters in the nuclear spin Hamiltonian can be calculated ab initio as electronic structure properties of the molecule. The theoretical foundation for this calculation is well-established for closed shell molecules [1]. Here we present a natural extension of Ramsey’s theory to molecules with an arbitrary electronic spectrum [2]. This includes paramagnetic systems with a degenerate ground state of spin or spin-orbit character, or systems where this degeneracy is lifted by a small zero-field splitting. In each case the chemical shift dependends on the thermal occupation of these [1] Gryn’ova, G., Marshall, D. L., Blanksby, S. J. and Coote, M. L. “Switching electronic states and becomes Radical Stability By pH-Induced Orbital therefore a thermodynamic Conversion” Nature Chemistry 2013, 5, quantity. It is also shown that the 474 -481. paramagnetic shift of a degenerate state can be expressed as a contraction of Zeeman and hyperfine coupling tensors, of all ranks required 4:30pm – 4:45pm by the size of the degeneracy.

References NMR Chemical Shift in [1] N. F. Ramsey, Phys. Rev. 78, 699 (1950) molecules with a (quasi)- degenerate Ground State [2] W. Van den Heuvel, A. Soncini, Phys. Rev. Lett. 109, 073001 (2012); A. Soncini, Authors W. Van den Heuvel, J. Chem. Phys. 138, 021103 (2013); W. Van den Heuvel, A. Dr Willem Van Den Heuvel, Dr Alessandro Soncini, J. Chem. Phys. 138, 054113 (2013). Soncini The University of Melbourne

Biography Willem Van den Heuvel obtained a PhD in Chemistry from the University of Leuven, Belgium. He is currently a McKenzie Postdoctoral Fellow at the University of Melbourne, working in the group of Alessandro Soncini.

40 www.physchem2013.com.au 4:45pm – 5:00pm Abstract The Far-IR/THz beamline at the The THz/Far-IR Beamline at the Australian Synchrotron is coupled Australian Synchrotron to a 9-chamber Bruker IFS125HR FT spectrometer equipped with a Authors variety of optical components which can cover the spectral range from 10 Dr Courtney Ennis 1, Dr Christopher Medcraft 2, Andy Wong 3, Ruth Plathe1 to 5000 cm-1; this instrument can offer an optimum unapodized resolution of 1. The Australian Synchrotron, ≥ 0.00064 cm-1. Experiments from a 2. Center for Free-Electron Laser Science, variety of fields such as atmospheric 3. Monash University and astrophysical science, geology, electrochemistry, nano-materials Biography as well as biology have been Courtney is the newest member successfully conducted at the of the THz/Far-IR Beamline at the beamline. Australian Synchrotron; returning There is a range of instruments home to join the team in November to accommodate the diverse 2013. Courtney earned his PhD at requirements of the User community. The University of Western Australia For the gas-phase, room-temperature (2009); investigating reactive species gas cells with multiple-pass optics, formed via fast-particle impact one of which can be coupled to a of simulated astrophysical ices. A furnace to study reactive species; postdoc position at the University of there is also a multiple-pass gas Hawai’i (Ralf Kaiser) followed where cell which can be cooled to liquid Courtney studied the chemical nitrogen or helium temperatures processing of planetary ices and in order to study aerosols and cold the degradation of aerospace gases. Condensed-phase Users have polymers with keV particles. At access to a cryostat and a grazing University College London (Steve incidence angle and a near-normal Price) he was project leader for the accessory to study condensed construction of a new apparatus phase systems, thin films and surface to study the reactions between interactions. molecular radicals (formed via laser photo-detachment of pure anion The synchrotron infrared light offers beams) and a target solid; mimicking a S/N advantage over conventional interstellar dust grain chemistry and thermal sources, and this advantage also industrial plasma deposition varies to a great degree upon the processes. With his new Fellowship spectral range and the resolution at the AS, Courtney will participate required by the experiment. In in the installation of the new laser this paper, the capabilities and systems for gas-phase photolysis and performance of the Far-IR beamline time-resolved spectroscopic studies, at the Australian Synchrotron will and develop the Beamline’s surface be presented as well as some science infrastructure to carry out applications undertaken at the astrochemistry experiments for his beamline, and future developments allocated research. such as laser photolysis & pyrolysis, and high-pressure diamond anvil cells. 41 www.physchem2013.com.au 5:00pm – 5:15pm 5:15pm – 5:30pm

Electronic energies, molecular Super-resolution localization structures and frequencies microscopy of transfected by systematic molecular cells, starved cells and fragmentation mitochondria

Authors Authors Prof Michael Collins Dr. Toby Bell, Donna Whelan, Georg Australian National University Ramm , Markus Bach, Aaron Brice, Dr Greg Moseley Biography Monash University

Michael Collins graduated from the Abstract Department of Theoretical Chemistry The past decade has seen the at Sydney University. After some development and application years postdoctoral experience in of a range of visible light based the UK and USA, he has been a techniques, known as super- researcher at the ANU. His main resolution microscopy, capable of interests in recent years have been in generating fluorescence images the dynamics of chemical reactions with resolutions inside the diffraction and the molecular potential energy limit of the imaged light. One surfaces that govern that dynamics. widely used approach is based on the detection and ‘localisation’ of Abstract emission from single molecules. Of A new version of systematic the many variants of localisation molecular fragmentation is presented microscopy, direct stochastic optical which provides a hierarchy of reconstruction microscopy (dSTORM) estimates for the energy, structure, is the most straightforward.(1) It vibrational frequencies and other takes advantage of fluorescence properties, of large molecules intermittencies (switching between with a computation time that dark (non-emissive) and light scales linearly with the size of the (emissive) states) of single molecules molecule. This method is combined to obtain spatially isolated intensity with an algorithm which ensures images of single molecules. Switching that the evaluation of the fragment between light and dark states is compositions is efficient for very large achieved via a balance of laser flux, molecules. The method is illustrated pH and a reducing buffer. using a number of examples: Protein structures derived from NMR We have recently implemented a spectroscopy and evaluation of home built dSTORM set-up using off the binding energies of large water the shelf components for a fraction clusters. With this approach, the of the cost of a commercial system. molecular potential energy surface We have developed new as well (PES) of very large systems can be as optimised existing, fixation and accurately approximated in terms labelling protocols(2) for imaging of PESs of relatively small molecular microtubules, actin filaments and fragments. mitochondria in a range of cells. 42 www.physchem2013.com.au Our dSTORM set-up and protocols Fig.1: dSTORM image of microtubules have led to images with resolutions in labelled with Alexa647 in a fixed HeLa cell. the tens of nanometre range. Cross-sections of microtubule filaments clearly show the sub-diffraction resolution achievable. We have now applied our set-up to study a range of biochemical systems. We have imaged microtubules in cells transfected to express proteins associated with Rhabdovirus and show that transfection leads to a dramatic ‘bundling’ effect of the cell’s microtubules. We have imaged starved cells and revealed the presence of sub-diffraction sized autophagosomes. These measurements highlight the ability of localisation super-resolution microscopy, particularly the dSTORM variant, to observe sub-diffraction features in cells and address, in a striking and direct fashion, important biological systems.

References (1) S. van de Linde, S. Wolter, and M. Sauer, Australian Journal of Chemistry, 64, (2 011) 5 0 3 - 511.

(2) S. van de Linde, A. Loschberger, T. Klein, M. Heidbreder, S. Wolter, M. Heilemann and M. Sauer, Nature Protocols, 6, (2011), 991-1009.

43 www.physchem2013.com.au Thursday 5 environment affect properties – which is often hidden in ensemble December 2013 measurements. In this talk I will present results from transient absorption experiments performed with diffraction limited spatial resolution. These measurements allow

Plenary Session us to study single nanostructures, and provide information about 9:00am – 9:45am their dynamics that is washed out in ensemble experiments. The systems Ultrafast Studies of Single that have been investigated include Metal and Semiconductor metal nanowires and nanoparticles, Nanostructures II-VI nanowires and carbon nanostructures. The time scales range from a few hundred fs to a few ns. The Prof Greg Hartland results provide detailed information University of Notre Dame, USA about how these materials interact with their environment, and trapping Biography and recombination of electrons and Prof. Hartland received a B. Sc. holes in semiconductor nanowires. (Hons.) from the University of Transient absorption images can Melbourne in 1985, and a Ph. D. also be collected, and provide from the University of California, Los information about the spatial Angeles in 1991. He joined the faculty variation of the dynamics, and at the University of Notre Dame in how the charge carriers move in a 1994, after postdoctoral studies at nanostructure. the University of Pennsylvania. His research interests involve using novel optical techniques to study single nanoparticles, with a goal of 9:45am – 10:00am understanding how these materials interact with their environment. He is a Senior Editor for the Journal The Photon of Persuasion: of Physical Chemistry A/B/C, and Influencing Branching Fractions is on the Editorial Advisory Board in the Photodissociation of of Physical Chemistry Chemical H2CO Physics. Prof. Hartland is a Fellow of the American Association for the Authors Advancement of Science (2009), M. S. Quinn, B. K. Nauta, S. H. Kable and an American Chemical Society The University of Sydney F e l l ow (2011). Biography Abstract Mitchell is a second year PhD student Single particle spectroscopy with Scott Kable at the University of is a powerful tool for studying Sydney working on a variety of Scott's nanomaterials. It is capable of reaction dynamics projects. Today he revealing information about how will be presenting recently obtained differences in size, shape and data on roaming in formaldehyde. 44 www.physchem2013.com.au Abstract By exciting different vibrational modes in a molecule, is it possible to direct a molecule to dissociate via a selected pathway? We are currently investigating the effects of pumping different vibrational modes; specifically the C-H symmetric and anti-symmetric stretches, in the photodissociation of formaldehyde. Formaldehyde has been a very well studied molecule in the study of spectroscopy and reaction mechanisms. Indeed, it was the Fig 1: Schematic of the relevant reaction first molecule where an alternate pathways in formaldehyde. The two pathway to molecular products was arrows depict the two exciting photons, first discovered and characterised. here the formaldehyde C-H stretch is [1] This alternate pathway, labelled excited in the ground state before a second laser pulse promotes it to S1. “roaming”, is closely coupled to the H + HCO barrierless dissociation pathway. However the molecule has insufficient energy along the C - H bond to fully dissociate and is held together by van der Waals forces until the ‘roaming’ hydrogen atom abstracts the hydrogen from the formyl co-fragment to form H2 + CO. Furthermore, roaming reaction pathways have been proposed and/ or observed in a number of systems since and it is thought that there may be a roaming pathway for each barrierless dissociation pathway. Fig 2: Photofragmentation spectra [2] This talk will examine the effects of formaldehyde. (a) is the spectrum obtained when the anti-symmetric C-H of exciting different C-H vibrational stretch is pumped in S0 before excitation modes on the branching fraction to S1. (b) is the standard phofex spectrum between the roaming and TS reaction from ground state S0 to S1. pathways. Velocity map imaging experiments, depicted in Figure 1, will References examine the effect of exciting the [1] Townsend et al. Science, 306 (2004) C-H stretch in both the ground (S0) and excited states (S1). [2] Bowman et al. Ann. Rev. Phys. Chem. 62 (2011) and references therein.

45 www.physchem2013.com.au 10:00am – 10:15am order to utilise the electrochemical potential created. However a ‘Hot’ Photo-induced Electron consequence of the initial non- radiative relaxation process is that Transfer excitation energy above the band gap of the absorbing species is Authors wasted as heat. We have been Prof Ken Ghiggino1, Prof Steven Langford2, investigating molecular donor- 1 Mr Ben Robotham acceptor molecular arrays that have higher electronic excited 1. The University of Melbourne, 2. Monash University states that are sufficiently long-lived (picoseconds) to undergo electron

Biography transfer to a closely associated acceptor before the initial thermal Prof Ghiggino is Masson Professor relaxation process occurs. The of Chemistry at the Unversity of rates and mechanisms of such ‘hot’ Melbourne. He is a PhD graduate of electron transfer and subsequent the University of NSW and undertook relaxation processes have been postdoctoral studies at the University resolved by femtosecond transient of Southampton prior to joining the spectroscopy. The implications of University of Melbourne. His research the results for improving the overall covers many aspects of fundamental light energy conversion efficiency in and applied photochemistry and artificial photosynthetic systems will molecular spectroscopy. He is a past be discussed. Chair of the RACI Physical Chemistry Division and the recipient of the RACI The second singlet excited (S2) Physical Chemistry Division Medal states of some metal centred and the RACI Australian Polymer porphyrins have lifetimes of a Medal. few picoseconds that is sufficient for fast electron transfer to Abstract compete with intramolecular Photo-induced electron transfer non-radiative relaxation. For zinc processes are primary events in tetraphenylporphyin complexes natural photosynthesis and are the with fullerene and with short- basis for the successful operation bridged covalently linked core- of artificial photosynthetic systems, substituted amino naphthalene thin film photovoltaic cells and diimide acceptors, S2 electron other opto-electronic devices. In transfer is a dominant process. [1] the normal course of events photo- In the latter case the initial ultrafast excitation of the electron donor- electron transfer from S2 is followed acceptor pair is followed by rapid by charge recombination to reform relaxation to the lowest vibrational S1 that subsequently undergoes levels of the first excited electronic a further slower electron transfer state before the electron transfer process to the acceptor. These process occurs. Much attention results have now been extended has been paid to increasing to supramolecular complexes of the subsequent rate of charge the zinc porphyrin with pyridine separation while retarding the and isoquinoline functionalised charge recombination process in naphthalene diimides where 46 www.physchem2013.com.au electron transfer processes are again He joined the academic staff in the observed but where the coordinating School of Chemistry and Physics at linker and solvent play major roles the University of Adelaide in 2010. in determining the mechanisms operating in each case. The range Abstract of energy and electron transfer The performance of organic processes that occur following photo- electronic devices made from excitation of arrays consisting of tin conjugated polymers is sensitive tetraphenylporphyrin with covalently to the nano-scale morphology attached naphthalene diimides and of the polymers. But modelling supramolecular phenolate/BODIPY the structural and electronic motifs will also be presented. properties of conjugated polymers on length scales that are relevant [1] B. Robotham, K. A. Lastman, S. J. Langford, K. P. Ghiggino, J. Photochem. to device performance – from the Photobiol. A: Chem., 2013, 251, 167-174; S. molecular level to the 100-nm scale K. Sugunan, B. Robotham, – is challenging. This talk will discuss coarse-grained computational models that we have developed to study the self-assembly of the 10:15am – 10:30am nano-scale structure of conjugated polymers and the impact of polymer Modelling Nano-Scale structure on functional properties Structure and Energy Transfer such as energy transport that are important in devices like organic solar in Conjugated Polymers cells. The talk will focus on our studies of the widely used conjugated Authors polymer poly(3-hexylthiophene) Dr David Huang, Patrick Tapping, Kyra (P3HT) and will compare the Schwarz, Scott Clafton, Dr Tak Kee computational results obtained with The University of Adelaide ultrafast time-resolved spectroscopic measurements. Biography Dr David M Huang is a Lecturer in Chemistry at the University of Adelaide. He received his BSc Keynote Session degree (Hons I and University Medal) in Physical Chemistry from the University of Sydney. He was 11:00am – 11:30am awarded a Fulbright Scholarship to undertake postgraduate studies Shearing nanoconfined fluids in the United States and obtained his PhD in Theoretical Chemistry Prof Debra Bernhardt from the University of California, The University of Queensland Berkeley. After a stint as a scientific copy editor for Springer-Verlag, he Biography carried out postdoctoral research at the University of Lyon, then at Debra Bernhardt (nee Searles) is a the University of California, Davis. Group Leader and Professor in the Australian Institute for Bioengineering 47 www.physchem2013.com.au and Nanotechnology and School of Molecule simulations can provide Chemistry and Molecular Biosciences insight into their behaviour that at The University of Queensland. She might not be easily assessable using is recognised for her contributions to experimental techniques. We show nonequilibrium statistical mechanics how nonlinear response theory can and thermodynamics including be applied to these systems and how development of fluctuation theorems it can be used to improve the results and studies of nonequilibrium systems obtained from simulations, where and confined fluids. Her research nonlinearity sets in at relatively low employs a range of theoretical fields. approaches, nonequilibrium molecular dynamics simulations and Study of lubrication is an area where quantum chemical calculations. changes in behavior due to flow is These techniques are used to develop important. In many cases lubrication a fundamental understanding of occurs at high strain rates and under matter and study applications high confinement. In this work we including transport in nanopores, use nonlinear response theory and fluctuations, material design, gas nonequilibrium molecular dynamics separation, and sustainable energy. techniques to evaluate the response of a fluid in a nanopore to the Authors application of shear. The movement Debra J. Searlesa,b, Stefano Bernardia, of the boundaries in opposite Sarah J. Brookesc directions induces the shear. The viscous heat generated inside the a. Australian Institute for Bioengineering pore is removed by a thermostat and Nanotechnology, University of applied exclusively to the atomic Queensland, Brisbane, Qld 4072, Australia. walls, leaving the dynamics of the b.School of Chemistry and Molecular fluid as realistic as possible. Biosciences, University of Queensland, Brisbane, Qld 4072, Australia. c.Queensland Micro- and Nanotechnology Centre and School of Biomolecular and Physical Sciences, 11:30am – 11:45am Griffith University, Brisbane, Qld 4111, Australia. Adiabatic energy surfaces:

Presenting and Corresponding Author the interplay between E-mail Address: [email protected] electronic coupling and electron-vibrational coupling Abstract that controls chemical Fluids in small nanopores have reactivity, spectroscopy, properties that differ from bulk fluids and the development of at the same state point due to the restriction of motion and layering entanglement effects, especially close to the wall. Of particular interest is their Authors behaviour when they are undergo Noel S. Hush1, Jeffrey R. Reimers2, Laura K. 3 4 flow, and this is relevant to a range McKemmish , Ross McKenzie of phenomena and applications. 1. School of Molecular Biosciences, The 48 www.physchem2013.com.au University of Sydney, Sydney, NSW 2006 interaction J to yield upper and Australia. lower adiabatic potential-energy E-mail: [email protected] surfaces. For 2J<λ, the lower surface 2. School of Chemistry, The University of is symmetry-broken (double welled), Sydney, 2006, NSW, Australia. and a general picture of thermal 3. Research School of Chemistry, The and optical (intervalence) transfer Australian National University, Canberra emerges. Building on the insights of ACT 0200 Australia. Michel Polanyi, this approach links 4. School of Mathematics and Physics, The in with general theories of chemical University of Queensland, Brisbane, QLD reaction dynamics– for example 4072 Australia from proton transfer to inversion (e.g. ammonia, for which the resonance Biography energy is ten times that of benzene), Noel Hush graduated from the and understanding of ground state University of Sydney with B.Sc. (Hons) geometries (c.f. Walsh “rules”). This and M.Sc degrees in 1945 and 1948. is illustrated by application to the In 1949, he accepted an invitation ground states of a series of molecules as Lecturer in Physical Chemistry at ranging from BNB and the Creutz- the University of Manchester, in the Taube ion to the ionized bacterial Department restructured by Michael photosynthetic reaction centre to Polanyi. He moved to the University of the molecular conductor Alq3 used Bristol in 1955, also holding numerous in OLED and other devices. The visiting appointments in the US, quantum-mechanical entanglement, and in 1971 returned to Sydney as i.e., the non-intuitive intrinsic aspect Professor of Theoretical Chemistry, of quantum phenomena (which the first such appointment providing manifest, e.g., the EPR paradox), undergraduate to postdoctoral resulting from adiabatic coupling teaching in the subject in Australia. is calculated. Thus a remarkable As Emeritus Professor since 1989, he unification of very diverse chemical has continued to work in the area phenomena can be achieved in of quantum chemistry on problems terms of the fundamental quantities of structure and dynamics. He is a J, λ, and a possible reaction energy Fellow of the Australian Academy change E0. of Science and the Royal Society of London and is a Foreign Member of Key Words the American Academy of Arts and Vibronic coupling, electron transfer, Sciences and the US Academy of isomerization, aromaticity, entanglement, Sciences. His most recent award is Born-Oppenheimer breakdown, potential-energy surfaces the biennial Ahmed Zewail Prize for Molecular Science in 2013.

Abstract Initial and final states of electron transfer systems can be represented by two-site diabatic energy surfaces generated through electron- vibrational interaction of strength λ. These are coupled by the resonance 49 www.physchem2013.com.au 11:45am – 12:00pm reaction in question. In many cases it is assumed that inter-system crossing Spin-system crossing points in can occur readily and does not hinder the reaction. We have carried reaction mechanisms out a number of studies in which we have determined the location and Authors energy of these inter-system crossing Brian F Yates1, Miranda F Shaw2, Alireza points. In this presentation I will Ariafard3, David S McGuinness4, Robert 5 discuss the importance (or otherwise) Robinson of the spin-system crossing points 1. University of Tasmania, Private Bag 75 for reaction mechanisms, provide Hobart, TAS 7001, [email protected] examples from our recent work on catalytic polymerisation reactions 2. University of Tasmania, Private Bag and small molecule activation, and 75 Hobart, TAS 7001, currently Miranda. discuss different methods for their [email protected] evaluation and validation. 3. University of Tasmania, Private Bag 75 Hobart, TAS 7001, Key Words [email protected] Minimum energy crossing points, spin 4. University of Tasmania, Private Bag 75 system crossing Hobart, TAS 7001, [email protected] 5. University of Tasmania, Private Bag 75 Hobart, TAS 7001, [email protected]

Biography Professor Brian Yates is currently seconded to the Australian Research Council as an Executive Director. He spends one day a week at the University of Tasmania where he continues to head up an active research program in computational chemistry with particular applications to organometallic, inorganic and organic chemistry.

Abstract Low-lying energy levels with different spin states are ubiquitous in transition metal systems and they can play a role in many organometallic reactions. For example, in some cases the reagent might exist in a doublet ground state, but it is the quartet state which is the more reactive or which has a lower activation energy for the 50 www.physchem2013.com.au Keynote Session this criterion controversially excludes some otherwise apparent hydrogen 12:00pm – 12:30pm bonds whilst also identifying some unphysical hydrogen bonds. Our recent work highlights some of Are bond critical points really these controversial examples and critical for hydrogen bonding? shows that a regional analysis of the reduced electron density gradient Dr Joseph Lane provides a more chemically intuitive The University of description of hydrogen bonding. Waikato, New Zealand This regional definition of interactions overcomes the known caveat of Biography only analyzing electron density Jo obtained his BSc(Hons) and critical points, which raises the title PhD from the University of Otago question. Namely, is it the presence in 2005 and 2008 respectively. His of an electron density bond critical PhD and postdoctoral supervisor point that defines a hydrogen bond was Prof. Henrik Kjaergaard, now or the general topology in the region at Copenhagen University. In 2009, surrounding it? Jo was appointed as a Lecturer in Physical and Theoretical Chemistry at the University of Waikato and was subsequently promoted to Senior Lecturer in 2012. Jo has won several awards including an Early Career Research Excellence Award and an Emergent Teaching Excellence Award.

Abstract Hydrogen bonding interactions are of importance in a diverse range of applications. Consequently, the exact definition of what actually constitutes a hydrogen bond arouses passionate discourse amongst even the most mild-mannered chemists. One of the most popular theoretical approaches used to identify hydrogen bonding involves a topological analysis of the electron density: where chemical bonds, just like atoms, are assumed to be physical entities that can be located in three-dimensional space. Within this theoretical framework, the presence of a bond critical point between the donor and acceptor groups is considered evidence of hydrogen bond formation. However, 51 www.physchem2013.com.au Friday 6 Abstract Understanding the influence of December 2013 electrons in partially filled f- and dorbitals on bonding and reactivity is a key issue for actinide chemistry. This subtle question can be investigated Plenary Session using a combination of well-defined experimental measurements and 9:00am – 9:45am high-level theoretical calculations. Gas phase spectroscopic data are particularly valuable for the Probing Actinide Bonding using evaluation of theoretical models. Multiphoton Excitation and Consequently, the primary Photoelectron Spectroscopy objectives of our research program are to obtain gas phase spectra Prof Michael Heaven for small actinide and lanthanide Emory University, USA compounds. Development of the tools for recording such spectra is also Biography a component of this endeavor. To Michael C. Heaven received his B. Sc. complement the experimental effort in Chemistry in 1975 and his Ph. D. in we are investigating the potential for Physical Chemistry in 1979, both from using relativistic ab initio calculations the Queen Mary College, University and semi-empirical models to of London. After postdoctoral studies predict and interpret the electronic at University of London, England energy level patterns for f-element and Bell Laboratories, Murray Hill, compounds. NJ from 1979–1982, he became an Assistant Professor at the Department Multiple resonance spectroscopy of Chemistry, Illinois Institute of and jet cooling techniques are Technology, Chicago. In 1986, he being used to unravel the complex joined the Department of Chemistry, electronic spectra of Th and U Emory University as Associate compounds. Recent results for the Professor and was promoted to oxides, sulfide and halides will be Professor in 1992. From 1996–1998, he discussed. Systematic errors in the was Director of Graduate Studies and accepted values for the ionization from 2003–2009 Associate Chair of energies have been discovered, and the Department of Chemistry, Emory the patterns of electronic states for University. His research interests these molecules provide information include the electronic spectroscopy concerning the occupation of the of transient intermediates, energy 5f orbitals and their participation in transfer kinetics, intermolecular bond formation. forces, and unimolecular decay dynamics.

52 www.physchem2013.com.au 9:45am - 10:00am interpretation of unexplained complex decoherence phenomena Assignment of the Q-Bands of associated with Qx → Qy relaxation. Whilst most chlorophylls conform to the Chlorophylls: Coherence the Gouterman model and display Loss via Qx-Qy Mixing two independent transitions Qx (S2) and Qy (S1), strong vibronic Authors coupling inseparably mixes these Prof Jeffrey Reimers 1, Dr Zheng-Li Cai 1, Dr states in chlorophyll-a. This spreads Rika Kobayashi 2, Dr Margus Ratsep 3, Prof x-polarized absorption intensity Arvi Freiberg 3, Prof Elmars Krausz 4 over the entire Q-band system to influence all exciton-transport, 1. The University of Sydney, relaxation and coherence properties 2. Australian National University, 3. University of Tartu, of chlorophyll-based photosystems. 4. The Australian National University The fraction of the total absorption intensity attributed to Qx ranges Biography between 7% and 33%, depending on chlorophyllide and coordination, Professor Reimers learned and is between 10% and 25% for spectroscopy under the direction chlorophyll-a. CAM-B3LYP density- of Ian Ross and Gad Fischer functional-theory calculations of at ANU before modelling the the band origins, relative intensities, thermodynamics and spectroscopy vibrational Huang-Rhys factors, and of water under Bob Watts. He vibronic coupling strengths fully learned semiclassical simulation support this new assignment. methods at UC San Diego under the direction of Kent Wilson and Rick Heller before moving to the University of Sydney in 1985. He has received the HG Smith Medal of the RACI and been elected as a Fellow of the Australian Academy of Science for his analyses of the operation of bacterial photosynthesis and of synthetic molecular electronic devices. He is currently Chair of the Physical Chemistry Division of the RACI.

Abstract We provide a new and definitive spectral assignment for the absorption, emission, high- resolution fluorescence excitation, linear dichroism, and/or magnetic circular dichroism spectra of 32 chlorophyllides in various environments. This encompases all data used to justify previous assignments and provides a simple 53 www.physchem2013.com.au 10:00am – 10:15am by the coherence of the incident light [2–5]. Indeed, energy transport Quantum enhancement of is quite different in spectroscopic experiments driven by femtosecond steady-state light harvesting in laser pulses than it is in natural sunlight sunlight. In particular, sunlight is stationary and incoherent for all Dr Ivan Kassal practical purposes, meaning that The University of Queensland any molecular system excited by it will be in a time-independent Biography steady state, with a density matrix Dr Kassal graduated from Stanford almost completely diagonal in the University in 2006 with degrees in energy basis [2]. I’ll discuss how chemistry and philosophy. In 2010, continuous transport proceeds he received his Ph.D. in chemical through this steady state, and how to physics from Harvard University, for calculate it efficiently. In particular, a thesis exploring the applications finding the steady state—and all of quantum computing to problems associated observables such as the in chemistry. Since 2011 he has been efficiency—is dramatically simpler at the University of Queensland as a than calculating the complete time- holder of a UQ Postdoctoral Research evolution followed by ensemble Fellowship, focusing on quantum averaging. Instead, the problem effects in biological systems and the reduces to finding the nullspace of a dynamics of energy transport in light simple, Markovian Liouvillian. In other harvesting complexes. words, neither wavelike transport nor non-Markovian effects—which are Abstract important to understanding ultrafast experiments—have an influence on Photosynthetic organisms harvest steady-state transport. light through large antenna complexes composed of many However, even though there is chlorophyll molecules supported no wavelike transport in sunlight by protein backbones. Recent and the process might therefore experimental studies have found appear completely incoherent, that energy is transported through the underlying quantum dynamics antenna complexes, and onward to can nevertheless influence the the reaction centre, in a coherent, overall (incoherent) rates [4]. I will wavelike manner [1]. Not only was give several examples both of this surprising—quantum effects model systems and of natural light- were thought unable to survive harvesting complexes where the for so long in biological systems at underlying coherence enhances room temperature—but it also led to the transport efficiency. From these speculation that evolution optimised examples, we can infer principles photosynthesis to take advantage of of quantum enhancement that can some sort of quantum enhancement. guide the design of more efficient artificial light harvesting in sunlight. I’ll describe some of the quantum effects in light harvesting, with a special focus on the role played

54 www.physchem2013.com.au References Hughes Predoctoral Fellow. After a [1] For example: Engel et al., Nature, 446, Department of Energy Distinguished 782 (2007); Panitchayangkoon et al., Proc. Postdoctoral Fellowship, she joined Natl. Acad. Sci. 107, 12766 (2010); Collini et Case Western Reserve University al., Nature, 463, 644 (2010). to pursue the research in ultrafast energy conversion by molecular [2] Jiang and Brumer, J. Chem. Phys., 94, systems that she has continued at 5833 (1991); Mančal and Valkunas, New Auckland. Recent awards include a J. Phys., 12, 065044 (2010); Brumer and Shapiro, Proc. Natl. Acad. Sci., 109, 19575 National Tertiary Teaching Excellence (2012). Award (2013).

[3] Fassioli, Olaya-Castro, and Scholes, J. Abstract Phys. Chem. Lett., 3, 3136 (2012). Solar energy is the key source of renewable energy that will meet our [4] Kassal, Yuen-Zhou, and Rahimi-Keshari, J. Phys. Chem. Lett., 4, 362 (2013). current and future global energy demands. Research is advancing [5] Jesenko and Žnidarič, J. Chem. Phys., on many fronts to make collecting, 138, 174103 (2013). storing and using energy in the form of light a reliable, efficient, inexpensive and clean technology. In our lab, we are using laser spectroscopy techniques to explore Keynote Session the potential of self-assembled, porphyrin-fullerene complexes as 10:45am - 11:15am the active light harvesting and initial charge-separation components Harnessing the Power of for devices that convert light to a the Sun – Self-Assembled quasi-stable charge-separated state. Advantages of these Porphyrin-fullerene Complexes complexes include simpler synthesis, as Functional Components wide absorption across the visible spectrum, and the relatively low A/Prof Cather Simpson reorganization energy of fullerenes. The University of Auckland, New Multi-step electron transfer steps can Zealand be designed into these compounds to extend their charge-separated Biography state lifetimes into practical Cather joined The University of timescales. Here we report the Auckland in 2007 to establish photodynamics of several sets of and direct the Photon Factory, calix[4]arene-linked bisporphyrin- a new multi-user ultrafast laser fullerene complexes intended to and microfabrication facility. test hypotheses about structure- Her appointment is held jointly in function relationships. Our primary Physics and Chemistry, and she tool is ultrafast transient absorption is a member of the MacDiarmid spectroscopy in the visible and Institute for Advanced Materials near-IR spectral regions. Following and Nanotechnology. She earned photoexcitation of the porphyrin, her Ph.D. in the USA as a Howard the initial charge separation step occurs within the first few tens of 55 www.physchem2013.com.au picoseconds. In these mechanistic Chemistry including nanoparticles, studies, charge recombination is in bioinorganic chemistry and soil the nanosecond range. The use of chemistry. a secondary donor as a porphyrin ligand extends the charge-separated Abstract state lifetime, but not in through The properties of metal clusters can the anticipated mechanism. differ significantly from that of bulk Initial studies of novel solid-state materials and are often dependant porphyrin-fullerene constructs on not only the composition but show the effects crystal packing on also the size of the cluster.[1] As a the electron transfer process. The result, cluster based materials are results are discussed with reference increasingly being investigated for to the development of similar self- their reactivity and catalytic activity assembled architectures as useful which may be enhanced due to their solar energy harvesting complexes. high surface-to-bulk ratio.

11:15am - 11:30am

Reactivity of Gallium Nano- clusters

Dr David Henry Ga12Al Ga12C

Murdoch University Density functional theory is used in Biography this study to investigate the structures, Dr Henry obtained his PhD in Physical stabilities and reactivity of doped Organic Chemistry from Deakin gallium nanoclusters, Ga12X (X = B, C, University in 1998 studying the kinetics N, Al, Si, P, Ga, Ge, and As). Gallium of hydrogen atom transfer from exhibits a strong preference for organotin hydrides to carbon centred formation of Ga2 subunits within both radicals using both theoretical and the bulk structure and in the structure experimental methods. He then had of small clusters.[2] This tendency a 3 year post-doctoral fellowship significantly contributes to the at ANU in the group of Prof. Leo general preference for decahedral Radom (ANU) studying radical symmetry in Ga12X clusters because thermochemistry and reactivity. it facilitates the formation of five Ga2 Following this he then spent 7 years subunits in the equatorial inter-ring with the group of Prof. Irene Yarovsky region. Furthermore, in all of the at RMIT University working on a studied cases, doping of the Ga13 range of projects including, polymer cluster leads to increased stability. coatings, Langmuir monolayers Generally the endohedrally doped and nanoparticles. He is currently a isomers are either lower in energy or lecturer in Chemical and Analytical close in energy to the isomers with Sciences at Murdoch University the dopant at the surface of the (Western Australia,)with research cluster. Endohedral Ga12C is the most interests in Physical and Analytical stable cluster and exhibits the most 56 www.physchem2013.com.au Jellium-like orbital structure. Trends References in vertical ionization potentials and [1] Clusters and Nano-Assemblies, 2005, electron affinities can be explained (Eds. P. Jena, S. N. Khanna, B. K. Rao) in terms of the interactions in frontier (World Scientific: Singapore). orbitals and generally adhere to the predictions of the Jellium model. [2] Gaston, N.; Parker, A. J. Chem. Phys. Lett. 2011, 501, 375-378.

[3] Henry, D.J.; Szarek, P.; Hirai, K.; Ichikawa, K.; Tachibana, A.; Yarovsky, I. J. Phys. Chem. C 2011, 115, 1714-1723.

[4] Henry, D.J.; J. Phys. Chem. C 2012, 116, 24814-24823.

Key Words

Electron density isosurface for Ga12Al Cluster reactivity, regioselectivity, chemisorption, covalency Covalency in the surface bonds of Al12X clusters has previously been shown to be an important factor in determining the reactivity of clusters and the regioselectivity of surface interactions.[3] The Ga2 subunits of Ga12X clusters exhibit considerable covalency which can be tuned by the addition of dopants thereby offering considerable potential to Ga …C Ga Al…CO utilises these species as cluster based 13 12 12 2 catalysts.[4]

Ga13…H2

So far a number of favourable interactions between Ga12X species and small molecules have been identified and characterised including dissociation of diatomic molecules and chemisorption of CO2.

57 www.physchem2013.com.au 11:30am - 11:45am nanoparticles immobilized onto inert supports [5]. Metal clusters can Metal Clusters on Oxide be deposited from the gas phase as size selected clusters or by the Surfaces for Catalysis evaporation of metals or from the liquid phase when using chemically Authors synthesised nanoparticles [6, 7]. The Gunther Andersson 1, Gregory Metha 2, latter route offers the huge benefit of Vladimir Golovko 3 easy scale-up. Removal of ligands is often postulated as a necessary step 1. Flinders University, 2. University of Adelaide, for making the adsorption sites at the 3. University of Canterbury surface of the clusters catalytically active. Biography Gunther Andersson is Assoc. Prof The chemically made clusters for Physics and Nanotechnology are deposited from solution onto at Flinders University and strategic oxide surfaces by dip coating after leader of the Flinders Centre for application of various surface pre- NanoScale Science and Technology. treatments. We have found that He obtained his PhD from the the pre-treatment of the oxide University of Witten-Herdecke surface plays a crucial role in the (Germany) in 1998. After a Postdoc agglomeration during the deposition at the Eindhoven University of process. Technology (The Netherlands) in the field of organic light emitting After the deposition of the clusters, diodes he obtained his Habilitation the surfaces are characterised with in Physical Chemistry at Leipzig electron spectroscopy (metastable University (Germany) in 2006. In 2007 induced electron spectroscopy he moved to Flinders University. His (MIES), X-ray and UV photoelectron current research activities are in the spectroscopy (XPS and UPS)) as well field of catalysis with nano-clusters, as X-ray absorption spectroscopy. renewable energies and liquid These data are analysed with surfaces. assistance from detailed modelling that provides information about likely geometry and electronic Abstract structure. The characterisation allows determining whether or not clusters Gold particles with a size reduced agglomerate during deposition below 5 nanometres are known and post-deposition treatment and to be catalytically active [1-3]. what the electronic structure of the Moreover, it has been demonstrated deposited clusters is. It is assumed that the onset of catalytic activity that the electronic structure plays a of gold often coincides with the crucial role in the catalytic activity. loss of metallic properties of Au nanoparticles at around 1.5-2 nm. [1] M. Haruta, S. Tsubota, T. Kobayashi, H. This size-threshold is established for Kageyama, M. J. Genet and B. Delmon, both naked clusters prepared under Journal of Catalysis, 1993, 144, 175-192. UHV conditions [4] and chemically- synthesised well-defined metal

58 www.physchem2013.com.au [2] R. Meyer, C. Lemire, S. Shaikhutdinov Keynote Session and H. Freund, Gold Bulletin, 2004, 37, 72-124. 11:45am - 12:15am [3] A. A. Herzing, C. J. Kiely, A. F. Carley, P. Landon and G. J. Hutchings, Science, Photodissociation of small 2008, 321, 1331-1335. aromatic species in the gas- [4] M. Valden, X. Lai and D. W. Goodman, phase and liquid-phase Science, 1998, 281, 1647-1650. microdroplets [5] M. Turner, V. B. Golovko, O. P. H. Dr Adam Trevitt Vaughan, P. Abdulkin, A. Berenguer- University of Wollongong Murcia, M. S. Tikhov, B. F. G. Johnson and R. M. Lambert, Nature, 2008, 454, 981-983. Biography [6] D. P. Anderson, J. F. Alvino, A. Adam completed undergraduate Gentleman, H. A. Qahtani, L. Thomsen, and Honours at the University of M. I. J. Polson, G. F. Metha, V. B. Golovko Adelaide then a PhD at University and G. G. Andersson, Physical Chemistry of Melbourne. Next was a postdoc Chemical Physics, 2013, 15, 3917-3929. at University of California Berkeley/ [7] David P. Anderson, Rohul Adnan, Jason Lawrence Berkeley National Labs. He Alvino, Oliver Shipper, Baira Donoeva, commenced his independent career Jan-Yves Ruzicka, Hassan Al Qahtani, at the University of Wollongong Hugh. H. Harris, Bruce Cowie, and Vladimir in 2008 where he runs the Laser B. Golovko, Gregory F. Metha, Gunther G. Chemistry Laboratory and teaches Andersson, PCCP 2013, 15, 14806 – 14813. chemistry. His research focuses on understanding chemistry in combustion environments, liquid microdroplets and in the gas-phase using lasers, mass spectrometry and synchrotron techniques.

Authors Christopher S. Hansen, Phillip J. Tracey1, Bartholomew S. Vaughn1, Brendon J. Roberts1, Berwyck L. J. Poad1, Stephen J. Blanksby1 and Adam J. Trevitt1

1. Laser Chemistry Laboratory, School of Chemistry, University of Wollongong, NSW, 2522

Abstract Photons initiate chemical action by exciting molecules to more active bound states or by breaking bonds to create reactive products.

59 www.physchem2013.com.au Fundamental insights into these electrospray is sampled by a mass processes has, for example: spectrometer. This is done one droplet • led to a useful understanding at a time: one droplet, one laser of atmospheric photochemistry pulse, one spectrum. (like haze formation and ozone depletion/creation) The gas-phase and liquid-phase photodissociation spectra of • aided the mitigation of small aromatics are compared to inefficiencies in organic- probe the effect of the solvent. sensitized solar cells Dissociation in these systems can • directed targeted be facilitated by ground state photodynamic therapies in unimolecular rearrangement biological systems. following rapid interconversion from excited state(s) and this process is To make further inroads and master studied in both phases. Also, using the photochemistry underpinning the microdroplet apparatus, the these applications, fundamental fate of photogenerated phenyl questions remain to be answered and benzyl-type aromatic radicals – the particular directions of our is explored in various solvents. The research group are the wavelength droplet photodissociation apparatus dependent photodissociation allows rapid surveys of liquid-phase channels and photoproduct chemistry in seconds using only characterisation of molecules both in picolitres (pL) of sample. the gas and liquid phase. Key Words Two techniques will be described in Laser, radial chemistry, mass this presentation – one that couples spectrometry, photodissociation, tunable UV-vis laser radiation to a spectroscopy. linear ion trap for gas-phase action spectroscopy of ions and the second instrument unites single microdroplet generation techniques, laser photolysis and mass spectrometry for rapid-acquisition of liquid-phase action spectroscopy. Our new single- droplet desorption strategy is shown in the figure below where a single droplet impinges on a thin needle held at 2 kV. The subsequent

60 www.physchem2013.com.au 12:15 pm - 12:30 pm stabilised by a variety of ligands in solution. The encapsulation ligands Ligand-mediated control of the mediate the nanoparticle surface electron density and thus influence surface plasmon resonance in the optical properties of the surface metal nanoparticles generated plasmon resonance transition. This by laser ablation manipulation of the electronic structure of the nanoparticle surface Authors has implications for a variety of Prof Mark Buntine, Ashley Mulder, Rhys possible applications. However, the Tilbury, Michael Wolter, Melissa Werrett, ability to fully exploit potential end- Phillip Wright, Dr Max Massi, Dr Paolo use applications requires a detailed Raiteri understanding of the metal-ligand Curtin University binding preferences. We make use of Molecular Dynamic simulations to Biography explore these binding preferences Mark Buntine, FRACI C Chem, and report on the synergistic is President of the RACI. He is interplay of experiment and theory the Immediate Past Chair of the in aiding our understanding of the Physical Chemistry Division and ligand-mediated optical properties a former President of the South of the metal nanoparticles. Australian Branch and a member of the Executive Committee of the Australian and New Zealand Society for Mass Spectrometry. He is the 12:30pm -12:45pm Head of the Chemistry Department at Curtin University. Mark's research Roaming, roaming everywhere interests include the use of lasers to explore a variety of chemical Authors phenomena, augmented by ab Prof Scott Kable, A/Prof Meredith Jordan, initio computational chemistry Dr Klaas Nauta, Mr Mitchell Quinn, Mr studies. He is a recipient of the RACI's Kelvin Lee Rennie Memorial medal. Mark is a The University of Sydney foundation Director of the Advancing Science by Enhancing Learning in the Biography Laboratory (ASELL) project. He has Scott Kable is a professor of chemistry been awarded numerous university, at the University of Sydney. He state and national awards for his earned his PhD at Griffith University learning and teaching activities. and did 3 years post-doctoral Abstract research at Cornell University before returning to Australia at the University We report on the production and of Sydney in 1992. His research has characterisation (spectroscopic and been recognised by the Le Fevre microscopic) of metal nanoparticles Award of the Australian Academy generated by the Laser Ablation of Science, a JILA Fellowship, and a Synthesis in Solution (LASiS) approach. Fulbright Senior Fellowship in 2010. In particular, we generate the metal He is currently a member of the ARC nanoparticles encapsulated and College. Scott has been awarded 61 www.physchem2013.com.au several University and National two different roaming pathways Teaching Awards. in CH3CHO photodissociation, giving rise to two different energy Abstract distributions in the roaming CH4 + CO Reactions that occur near the products. These two distributions had energetic threshold can be very been misinterpreted previously as different to those where energy is evidence for roaming and transition in excess. The rate of a dominant state mechanisms instead of two reaction mechanism can be slowed, roaming mechanisms. While there which allows other processes to be is evidence for a third pathway via observed. These “near threshold” the conventional transition state, our processes are always present, but experiments demonstrate that it is a often obscured by the dominant minor pathway. mechanism, and can explain unusual kinetic behaviour, and the presence This is the first demonstration that of unexpected reaction products. multiple roaming pathways exist One such near threshold mechanism in the same molecule. It adds to in photodissociation is “roaming”, the growing belief that roaming in which two departing fragments mechanisms are ubiquitous and that orbit each other and re-collide in they may provide explanations for a different configuration. This gives many reactions with unexplained rise to unexpected photochemical kinetic behaviour. products, with an unusual distribution of energy. References [1] Houston and Kable, PNAS, 103, 16079 Roaming in acetaldehyde has been (2006) somewhat controversial in recent [2] Heazlewood et al, PNAS, 105 12719 years. Some time ago we published (2008) the first observation of roaming in acetaldehyde photodissociation. [1] [3] Rubio-Lago et al, PCCP, 14, 6067 Experimentally, the CO fragments (2012). were observed to be much colder than the same products formed via the traditional transition state mechanism. 15% of the CO yield was estimated to be due to roaming. More recent experiments probing the CH4 photofragment attributed roaming to be 85% of the CO yield. [2] Even more recently, a third group measured the product state distribution of the CO by the technique of ion imaging and inferred 10-20% roaming yield. [3]

In this talk, I shall demonstrate that all three previous experiments are valid, but that all three have misinterpreted the data. There are actually 62 www.physchem2013.com.au Plenary Session My group is studying the limit of performing molecular spectroscopy 1:45pm -2:30pm with a single molecular ion and a single atomic ion. Precise measurement of molecular ion Probing molecular ions with transitions has applications in both laser-cooled atomic ions astrochemistry and the measurement of possible time variations in A/Prof Kenneth Brown fundamental constants. I will Georgia Institute of Technology, USA present our work on determining the molecular ion mass by resolved Biography atomic sideband spectroscopy and Kenneth Brown is an Associate our progress towards measuring the Professor in the Schools of Chemistry vibrational overtones metal hydride and Biochemistry; Computational ions. Science and Engineering; and Physics at the Georgia Institute of Technology. He received his PhD from University of California, Berkeley 2:30pm - 2:45pm studying theoretical issues in quantum information in the group of Birgitta Resonance and Whaley. As a postdoctoral fellow Photoisomerization in Fluorescent at MIT, he worked on trapped ion Protein Chromophores: Reversible and NMR quantum information Photobleaching Rate and experiments in the group of Isaac Proximity to the Cyanine Limit Chuang. His current research interests are cold molecular ions and quantum Authors information. Dr Seth Olsen The University of Queensland Abstract

Laser-cooled atomic ions can Biography be exquisitely controlled at the Dr. Olsen was born and educated in quantum level. As a result, trapped the USA. He received a Bachelor’s atomic ions have been used to build of Science with Honours in physics extremely precise atomic clocks, at the College of William and quantum simulators of magnetic Mary in Virginia in 1997 and a PhD materials, and prototype quantum in Biophysics and Computational computers. This control can also Biology by the University of Illinois be used to sympathetically cool at Urbana-Champaign in 2004. His and probe co-trapped molecular research interests lie at the boundary ions. Current experiments with of physics, chemistry and molecular mixtures of molecular ions and biology and revolve around the laser-cooled atomic ions include transduction of energy by self- the measurement of chemical rates organizing molecular machines. at temperatures of a few Kelvin and precision spectroscopy of vibrational transitions.

63 www.physchem2013.com.au Abstract 2:45pm - 3:00pm The green fluorescent protein (GFP) and its natural and engineered Reactive Simulations of variants represent some of the most Carbonates in Water powerful tools of modern molecular and cellular biophysics. Reversible Authors photobleaching in GFP variants is a Dr Paolo Raiteri 1, Dr Chris Knight 2, Prof two-edged sword; on the one hand Greg Voth 2,3, Prof Julian Gale 1 it can complicate the acquisition and interpretation of fluorescence 1. Curtin University, images collected using these 2. Argonne National Laboratory, markers, on the other hand it has 3. James Franck Institute, and been exploited as a platform for new Computation Institute sensing and imaging technology development. Understanding the Biography reversible photobleaching process Dr Raiteri obtained his PhD from the of GFP variants is of interest for the University of Milano-Bicocca in 2003. development of new technologies, He successively moved to the group and also as an important model of Prof Parrinello at ETH Zurich, where system for understanding general he worked for 4 years as a research photobiological yield and control assistant. In 2008 Dr Raiteri joined problems. Structural data suggest Curtin University as a Early Career that, in many cases, reversible research fellow and he is currently a photobleaching is associated senior research fellow holding an ARC with photoisomerization and/or fellowship. phototitration of the chromophore of the protein.[1] Recently, new Abstract data have suggested that the rate of reversible photobleaching in Carbonates are ubiquitous materials some GFP variants is correlated the that can commonly be encountered charge-transfer dipole magnitude in everyday life in the form of associated with excitation of the anything from scale in domestic chromophore.[2] In this talk, I will and industrial appliances through show how these correlations can to as constituents of the exoskeleton be simply explained once it is of marine organisms. Despite its recognized that the chromophore abundance and importance of these proteins belongs to a well- a detailed understanding of known and very important class of the mechanisms controlling the organic chromophores: the cyanine dissolution and growth of carbonate dyes. The mechanism has profound materials is still out of reach. This implications for engineering the has in fact proven to be particularly properties of fluorescent proteins, challenging, both for experimentalists which I will discuss. and theoreticians, and only in recent years have atomistic pictures of the [1]. P. Dedecker et al. J. Am. Chem. Soc. early stages of nucleation of calcium 135 (2013) 2387. carbonate started to emerge1,2. In particular pH, which is known to play [2]. M. Drobizhev et al. Scientific Reports. a key role in controlling the delicate 2 (2012) 688. balance between growth and 64 www.physchem2013.com.au dissolution of these materials, References has been the main obstacle to [1] Gebauer D., Voelkel A., and Coelfen performing realistic simulations of H., 2008, “Stable Prenucleation Calcium carbonate materials and it has Carbonate Clusters”, Science, 322(5909), often been neglected or treated in pp. 1819–1822. approximate ways. [2] Wallace A. F., Hedges L. O., Fernandez-Martinea A., Raiteri P., Gale In this presentation we show a first J. D., Waychunas G. A., Whitelam S., application of reactive classical Banfield J. F., De Yoreo J. J., “Microscopic molecular dynamics simulations Evidence for Liquid-Liquid Separation to the case of calcium carbonate in Supersaturated CaCO3 Solutions”, dissolution and growth. Here the Science, accepted 24/06/13. reactivity is added through the MS- EVB formalism3 on top of carefully [3] Knight C., Lindberg G. E., and Voth G. calibrated empirical forcefields, A., 2012, “Multiscale reactive molecular dynamics”, Journal of Chemical Physics, which are known to reproduce the 137(22), p. 22A525. thermodynamic properties of the unreactive species4. This approach [4] Demichelis R., Raiteri P., Gale J. allows the advantages of quantum D., Quigley D., and Gebauer D., 2011, simulations (reactivity) to be “Stable prenucleation mineral clusters combined with those of empirical are liquid-like ionic polymers”, Nature simulations (speed) at the small cost Communications, 2, p. 590. of adding only few extra parameters to reproduce the reaction barrier. The reported results demonstrate how to the thermodynamic properties of the system can be accurately reproduced and and how the introduction of reactivity affects the early stages of nucleation and dissolution of calcium carbonate.

65 www.physchem2013.com.au 3:00pm – 3:15pm heavy, high d transition metals such as platinum and palladium Effective and ineffective that are usually active in hydrogen catalysis in other contexts. This work transition metal catalysis in examines an oft-neglected aspect reversible hydrogen storage of the role of the transition metal catalysts, namely rehydrogenation Dr Terry Frankcombe of the decomposition products. The Australian National University effect of catalyst atoms embedded in the surface of sodium hydride Biography has been investigated using DFT Terry Frankcombe completed his PhD methods, along with how the under the supervision of Prof Sean interaction with hydrogen molecules Smith at the University of Queensland changes. Dramatic and simply in 2002. He was a postdoc first at rationalisable differences are seen UQ, then with Geert-Jan Kroes at the between the behaviour of dopants University of Leiden. He held a Marie that are effective (Sc, Ti and V) and Curie Fellowship at the University of those that are not (Pt and Rh). The Gothenburg with Gunnar Nyman in results suggest that a “hydrogen 2007 before returning to Australia to pump” mechanism is active in the work with Michael Collins at ANU. rehydrogenating system. This is He was awarded an ARC Future one of the first studies to effectively Fellowship in 2010. rationalise the difference in activity of different transition metal dopants. Abstract One of the barriers to transitioning to a hydrogen-mediated energy economy is the lack of appropriate hydrogen storage technologies. One of the most popular potential storage systems is storing hydrogen as a complex metal hydride that decomposes on heating, but reconstitutes under hydrogen pressure (known as reversible hydrogen storage). Thermodynamic and gravimetric considerations point to using sodium alanate, NaAlH4, as the storage material. Doping with transition metal catalysts improves dehydrogenation kinetics and is essential for reversible hydrogen storage. Titanium was the first active catalyst discovered and remains one of the best. Light transition metal elements near titanium in the periodic table are also effective. What are not effective are the

66 www.physchem2013.com.au Keynote Session and MacDiarmid Institute for Advanced Materials and Nanotechnology, PO Box 600, Wellington 6140, New Zealand. 3:45pm - 4:15pm Abstract Ultrafast Probes of Free Charge Several characteristic lengths Photogeneration in Organic are central to free charge Photovoltaics photogeneration in polymer- fullerene organic photovoltaics. Dr Justin Hodgkiss Recent measurements suggest that Victoria University of Wellington, the observed ultrafast branching New Zealand between tightly bound charge pairs and separated charges Biography is linked to the spatial extent of excitons and polarons. We have Dr Justin Hodgkiss is a senior lecturer developed a series of time-resolved in Physical Chemistry at Victoria optical spectroscopy experiments University of Wellington, a Rutherford that resolve different properties of Discovery Fellow and a Principal bound and free charges, including Investigator in the MacDiarmid the characteristic length scales Institute for Advanced Materials and associated with the key branching Nanotechnology. Justin completed step. An underpinning capability his Ph.D. at Massachusetts Institute of all of our measurements is the of Technology in 2006 with Daniel sensitivity to carry out measurements Nocera, followed by post-doctoral at low enough laser excitation research at the University of intensity to mimic solar excitation Cambridge with Sir Richard Friend conditions. before returning to New Zealand in 2009. His research program exploits Using an ultrafast Kerr gate ultrafast optical spectroscopy photoluminescence spectrometer, to probe the optoelectronic we resolve substantial high-energy functionality organic semiconductors. emission from hot excitons prior His work on organic photovoltaics to energetic relaxation, which was recently recognized with the occurs predominantly on a sub-ps Young Scientist Prize from the Asian timescale. Consistent with quantum and Oceanian Photochemical chemical calculations, ultrafast Association. annihilation measurements show that excitons initially extend along Authors a substantial chain length with a 1 2 2 Justin Hodgkiss , Kai Chen , Alex Barker , volume approaching 20 nm3, prior 2 Shyamal Prasad to localization induced by structural relaxation. Moreover, we see that 1. School of Chemical and Physical Sciences, Victoria University of Wellington hot excitons are initially highly and MacDiarmid Institute for Advanced mobile and the subsequent rapid Materials and Nanotechnology, PO Box decay in mobility is correlated with 600, Wellington 6140, New Zealand. energetic relaxation. The relevance [email protected] of these measurements to charge 2. School of Chemical and Physical photogeneration is confirmed by our Sciences, Victoria University of Wellington measurements in blends. We find 67 www.physchem2013.com.au that charge photogeneration occurs 4:15pm - 4:30pm predominately via these delocalized hot exciton states in competition with Aerosol icing on the cake: IR relaxation and independently of temperature. spectroscopy of nanoscale particles By resolving the effect of temperature and excitation density on charge Authors recombination via transient Dr Evan Robertson1, Dr Chris Medcraft2, absorption spectroscopy in Mr Andy Wong2, Dr Chris Thompson2, polymer-fullerene blends, we are Prof Don McNaughton2, Dr Dominque 3 4 able to access a regime where all Appadoo , Dr Sigurd Bauerecker photogenerated charge pairs are 1. La Trobe University, frozen out following the primary 2. Monash University, charge transfer step and recombine 3. Australian Synchrotron, via tunneling. The exponential 4. Technische Universität Braunschweig, distance dependence of electron tunneling provides a sensitive probe Biography of the distance distribution of initial Dr Evan Robertson qualified for charge pairs. We show that the most his PhD at Monash University, then efficient blends are associated with worked as a post-doctoral researcher substantially longer initial electron- in laser spectroscopy with Prof. John hole pair distances, which may be Simons at the University of Oxford. linked to the delocalization of the In 2001, he returned to the School of primary excitation. Chemistry at Monash University to take up Logan and ARC research fellowships, followed by a lectureship. In 2009, he moved to La Trobe University where he leads a research group in optical spectroscopy manifested in two major areas: (1) laser-based spectroscopy directed towards understanding gas phase conformation and clusters of biomolecules; and (2) FTIR spectroscopy relevant to planetary atmospheric and interstellar chemistry.

Key Words Abstract Organic photovoltaics, ultrafast fluorescence spectroscopy, ultrafast Atmospheric aerosols scatter transient absorption spectroscopy. and absorb radiation, influence cloud formation and play a role in heterogeneous chemical reactions in the atmosphere, affecting the concentration and distribution of atmospheric trace gases.

68 www.physchem2013.com.au IR spectroscopy, with its acute smaller than around 5nm. These sensitivity to the chemical bonding measurements provide a means to environment, has been widely used to assess optical constants required for study clusters and aerosols. Recently, radiative forcing calculations in many a new generation of collisional contexts, including earth’s energy cooling cell designed by one of balance. our collaborators has created new possibilities for systematically studying aerosols generated by pulsed sequences of injections. We have 4:30pm -4:45pm used one of these cells, coupled to the Bruker IFS125HR spectrometer on Helium Nanodroplet the High Resolution Infrared Beamline at the Australian Synchrotron, for both Isolation Spectroscopy of high resolution gas phase studies Hydridotrioxygen and of its and for aerosol studies. Development Complexes with Dioxygen work on the cooling cell has made it possible for the first time to extend Authors these types of aerosol measurements Paul Raston1, Tao Liang 2, Gary Douberly2 to the crucial but hitherto unexplored 1. The University of Adelaide, far IR region. IR Spectra have been 2. University of Georgia measured for aerosols comprised of small organic and inorganic Biography molecules, and aerosols of water ice Paul Raston completed his provide a case study of how much undergraduate studies at Griffith may be learned from such spectra. University, after which he moved to the Cowboy State to pursue his Crystalline water ice particles in graduate studies at the University the nanoscale size regime were of Wyoming. During this time in the generated by rapid collisional group of David Anderson he focused cooling at temperatures ranging on the isolation and spectroscopy from 4-209 K. Their spectra have of radicals in solid hydrogen. He been measured in the far-IR region has been a Postdoc in the group of for the first time, using synchrotron Wolfgang Jäger at the University radiation, and also in the mid-IR of Alberta where he explored region. Spectral diagnostics, such as microscopic superfluidity in helium the ratio of surface related dangling and hydrogen clusters. More recently OH to interior H-bonded OH stretch Paul was a Postdoc in the group bands, reveal the manner in which of Gary Douberly at the University particle size depends on bath gas of Georgia where he investigated temperature and density, and on highly reactive species in helium water molecule concentration. nanodroplets, which he will talk Notably, the aerosol spectra show about today. He is currently at The significant differences compared to University of Adelaide where he previous thin film spectra. The particle has just begun a four year Ramsay size regime (3-150 nm) is such that Fellowship. scattering effects are negligible, and the onset of less crystalline behaviour may be observed for particles 69 www.physchem2013.com.au Abstract multiple isomers of cis - and trans- The hydridotrioxygen (HOOO) HO3-O2, corresponding to either radical and its deuterated analogue hydrogen or oxygen bonded van (DOOO) have been isolated in helium der Waals complexes. Comparisons nanodroplets following the in-situ to theory suggest that the structure association reaction between OH of the HO3-O2 complex formed and O2. The infrared spectrum in in helium droplets is a hydrogen- the 3500-3700 cm-1region reveals bonded 4A’ species consisting of bands that are assigned to the v1 a trans-HO3 core. The computed (OH stretch) fundamental and v1+v6 binding energy of the complex is (OH stretch plus torsion) combination approximately 240 cm-1. Despite the band of the trans-HOOO isomer. The weak interaction between trans-HO3 helium droplet spectrum is assigned and O2, non-additive red shifts of the on the basis of a detailed comparison OH stretch frequency are observed to the infrared spectrum of HOOO upon successive solvation by O2 to produced in the gas phase [E. L. form the larger clusters with n >1. Derro, T. D. Sechler, C. Murray, and M. I. Lester, J. Chem. Phys. 128, 244313 (2008)]. Despite the characteristic low temperature and rapid cooling 4:45pm - 5:00pm of helium nanodroplets, there is no evidence for the formation of a Can dianions make strong gas weakly bound OH-O2 van der Waals phase bases? complex, which implies the absence of a kinetically significant barrier in Authors the entrance channel of the reaction. Dr Berwyck Poad, Nicholas Reed, Dr There is also no spectroscopic Adam Trevitt, Prof Stephen Blanksby evidence for the formation of cis- University of Wollongong HOOO, which is predicted by theory to be nearly isoenergetic with the Biography trans isomer. Stark spectroscopy of the trans-HOOO species Dr Berwyck Poad is an ARC provides vibrationally averaged DECRA fellow at the University of dipole moment components Wollongong, focusing most of his that qualitatively disagree with attention on multiply charged anions. predictions obtained from CCSD(T) Berwyck completed his PhD with computations at the equilibrium, Prof. Evan Bieske at the University planar geometry, indicating a of Melbourne in 2009, before floppy complex undergoing large- undertaking post doctoral work at amplitude motion about the torsional The University of Wollongong and coordinate. Under conditions that then the University of California, San favour the introduction of multiple Diego. O2 molecules to the droplets, bands associated with larger H/DOOO- Abstract (O2)n clusters are observed shifted Multiply charged anions have been ~1-10 cm-1 to the red of the trans-H/ proposed as a route to create DOOO v1 bands. Detailed ab initio gas phase bases, potentially even calculations were carried out for stronger than the current strongest

70 www.physchem2013.com.au reported gas phase base, LiO- [1]. 5:00pm – 5:15pm The additional charge(s) present on a doubly (or multiply) charged system Rotational spectroscopy of leads to an increased proton affinity, but at the same time a reduced PANH and cyano substituted electron affinity. Computational PAH species studies probing the limits of gas- phase basicity concluded that to Authors create multiply charged anions that Prof Donald McNaughton 1, Dr Peter are both highly basic, but have a Godfrey 1, Prof Jens Uwe-Grabow 2, Dr positive electron binding energy “will Michael Travers 2, Michaela Jahn 2, David 2 be a challenge... even if multiply Dewald charged anions are considered 1. Monash University, [and] lithium hydroxide will be hard to 2. Gottfried-Wilhelm-Leibniz-Universität replace at the top of the gas-phase acidity scale” [1]. Biography

In this contribution, we present Don did his PhD at Monash University experimental evidence for in the last century and after a post deprotonation of per-deuterated doc at Sussex Uni in microwave and methane and deuterium by a dianion high resolution infrared spectroscopy “superbase,” demonstrating that it returned to Monash. Over his career is possible to generate dianions that he has branched out and is director behave as particularly strong gas of the centre for biospectroscopy at phase bases. Using electrospray Monash where the focus is the use of ionisation mass spectrometry, a FTIR and Raman microspectroscopy series of dianions originating from and imaging for investigating the para phenylenedipropiolic acid biochemistry of biological systems. have been generated in the gas Since 2006 he has renewed his phase and isolated within a linear interest in interstellar chemistry and quadrupole ion trap. Subsequent microwave spectroscopy, which is the ion-molecule reactions between the subject of this talk doubly deprotonated species and neutral reagents of known gas phase Abstract acidity have allowed the relative It has been postulated that polycyclic basisity of the dianion species to aromatic heterocycle (PAH) be bracketed, providing evidence variants containing one or more that one of the dianions generated nitrogen substituents, the polycyclic possesses a proton affinity in excess aromatic nitrogen heterocycles of the methanide anion (416.7 kcal/ (PANHs), may be responsible for mol) and is a good candidate for the variations in peak positions in IR strongest known gas phase base. interstellar emission features1. In order to provide data that could Reference eventually unambiguously confirm [1] Tian, Chan, Sullivan, Radom, Kass, PNAS the presence of such species in the 105 (22), 7647 – 7651 ISM we have measured and assigned the pure rotational spectra of the 2 and 3 ring PANHs2,3 employing Stark modulated millimetre wave 71 www.physchem2013.com.au absorption free jet spectroscopy and 5:15pm - 5:30pm FTMW spectroscopy of a supersonic rotationally cold molecular beam. Understanding electronic Given that some 40 cyano containing species have been identified in structures of molecules from the interstellar medium the spectra gamma-ray spectroscopy of the cyano-naphthalenes and cyano-phenanthrenes have also Author been recorded and assigned. Feng Wang Unlike the PAHs themselves these Swineburne University of Technology species have large dipole moments and quadrupole nuclei, leading Biography to intrinsically strong lines and Professor Feng Wang is a leading fine structure that assists in any theoretical chemist in molecular identification in spectra obtained electronic structures through from the ISM. For all species molecular spectroscopy. She has quadrupole coupling constants, been elected as Fellow of RACI and essential for full prediction of Fellow of AIP, working at the interface interstellar lines have been of chemistry and physics. For more determined. detials please see her staff website at

Given that no aromatic species have Abstract been identified in the interstellar medium the spectra of these Positrons are antimatter of electrons. molecules present an excellent Annihilation gamma ray spectra are opportunity for eventual identification used in a variety of fields including of aromatic species and further medicine and drug design, where insights into interstellar chemistry. positron emission tomography (PET) is used to monitor metabolic and other References biological processes, and in materials science, where positron annihilation [1] D. M. Hudgins, C. W. Bauschlicher, L. J. is used to characterize materials and Allamandola, Astrophys. J., 632, 316 (2005) material surfaces. It may provide an [2] D McNaughton, P. D. Godfrey, R. innovative way for the breakthrough D. Brown, S. Thorwirth, J.-Uwe Grabow, in the study of electron-electron Astrophys. J., 678, 309 (2008) interactions and ionization processes of molecules. In this presentation, [3] D. McNaughton, Peter D. Godfrey, the quantum mechanically study of J-Uwe Grabow, M K. Jahn and D A. spectra of annihilation gamma rays Dewald, FTMW and Millimetre Wave for molecules will be briefly reviewed. Spectroscopy of quinazoline, quinoxaline, phthalazine J. Chem. Phys. 134, 154305 The low-energy plane-wave- (2 011) positron approximation (LEPWP) [1] was developed to calculate the Doppler-shift of gamma-ray for molecules quantum mechanically. It was soon discovered that the calculated Doppler-shift of molecules were approximately 70-80% of the measurements [2-4], leading to the 72 www.physchem2013.com.au question: do all valence electrons of Keynote Session a molecule contribute equally to the Doppler-shift of gamma-ray? Follow 5:30pm- 6:00pm this direction, we studies alkanes and their derivatives, which leading to the development of a number Ab initio molecular dynamics of concepts such as positrophilic of molecules in strong laser electrons [5], the lowest occupied fields valence orbital (LOVO) [6], the mechanism for the determination Professor H. Bernhard Schlegel of the positrophilic electrons of the Wayne State University, USA molecules [7] and the concept of quality of profile (QP) to quantify the Biography agreement between calculated H. Bernhard Schlegel is Distinguished and measured gamma-ray profiles Professor of Chemistry at Wayne in the entire region rather than at a State University. After earning a BSc particular point [8]. from the University of Waterloo, Ont. (1972) & a PhD in Theoretical Organic References Chemistry at Queen’s University, [1] F. Wang, L. Selvam, G. F Gribakin and Kingston, Ont. Canada (1975), he was C. M Surko, J. Phys. B: 43, 165207(2010). a post-doctoral fellow with Kurt Mislow & Lee C. Allen at Princeton U. (1976) [2] F. Wang, X. G. Ma, L. Selvam, G. & with John A. Pople at Cargenie- Gribakin and C. M. Surko, Euro. Phys J D 66(4), (2012)107. Mellon U. (1977). He spent two years in industry as a computational chemist [3] D. G. Green, S. Saha, F. Wang, G. F. at Merck & Co. before accepting Gribakin and C. M. Surko, New J. Phys., a faculty position at Wayne State 14(2012)035021. University in 1980. Schlegel’s research explores potential energy surfaces for [4] F. Wang, X. G. Ma, L. Selvam, G. chemical reactions through the use Gribakin, and C. M. Surko, New J. Phys., 14 of molecular orbital calculations, & (2012) 085022. includes both method development [5] X. G. Ma and F. Wang, Radiat. Phys. & applications. The development of Chem., 85(2013)59-63. new algorithms addresses topics such as geometry optimization, searching [6] X. G. Ma and F. Wang, Radiat. Phys. for transition states, reaction path Chem., 89(2013)14-19. following and ab initio molecular dynamics. Schlegel is a Fellow of [7] X. G. Ma and F. Wang, J Phys. Soc. the American Chemical Society, (Jpn) (accepted, 2013). the American Association for the Advancement of Science & the Royal [8] X. G. Ma and F. Wang, (submitted, 2013). Society of Chemistry, & is a member of the International Academy of Quantum Molecular Science. Schlegel is an associate editor for the Journal of Chemical Theory & Computation. In 2013, he received the ACS Award for Computers in Chemical & Pharmaceutical Research. 73 www.physchem2013.com.au Abstract Short, intense laser pulses can deposit a substantial amount of energy in a molecule. Such highly energized molecules can undergo rapid rearrangements and dissociation. The effect of a strong electric field on the motion of a molecule can be simulated by ab initio classical trajectory calculations in the time- varying field. Our calculations show that if the molecule can be aligned in the field, very short and intense mid-IR pulses can cause the selective dissociation of stronger bonds in CF3Br+ and C6H5I2+, and can enhance the yield of higher energy HCl+ products in the fragmentation of formyl chloride cation, ClCHO+. A new, more accurate Hessian-based predictor-corrector algorithm for simulating classical trajectories of molecules in intense laser fields will also be discussed.

Key Words Ab initio molecular dynamics, strong field chemistry

74 www.physchem2013.com.au Poster Presentations

75 www.physchem2013.com.au Poster Session One

1 In silico investigation of inhibiting signaling molecules for bacterial quorum sensing using molecular modelling Marawan Ahmed, Stefanie Bird, Enzo Palombo, Kevin Prince, Feng Wang

2 Far-Infrared Absorption Spectra of Synthetically-Prepared Ligated Metal Clusters with Au6, Au8, Au9 and Au6Pd Metal Cores Jason Alvino, Trystan Bennett, A/Prof Greg Metha

3 Catalysis by design: H2-selective formic acid decomposition by zeolites Ruth Amos

4 A Phase Space Theory for Roaming Reactions Duncan Andrews, A/Prof Meredith Jordan, Prof Scott Kable

5 Femtosecond Laser Parameters Required for Optimal Laser Ablation of Bone Simon Ashforth, A/Prof Cather Simpson , Dr Jessica Costa

6 Twisted Aromatics as Potential Chromophores for Luminescent Solar Concentrators James Banal, Kenneth Ghiggino, Wallace Wong

7 Size consistency in Fragment Molecular Orbital Approach Coupled with Second Order Perturbation Theory (FMO-MP2) Dr Santiago Barrera Acevedo, Dr Ekaterina Izgorodina

8 Spatial imaging of fluorescence and photocurrent in thin film photovoltaics Ognjen Belic, Prof Ken Ghiggino, A/Prof Trevor Smith

9 Far-Infrared Absorption Spectra of Synthetically-Prepared, Ligated Metal Clusters with Ru3, Ru4, and AuRu3 cores Trystan Bennett, Jason Alvino, A/Prof Greg Metha

10 Thermodynamics of Alcohol and Water Binary Mixtures Quinn Besford, Dr Angus Gray-Weale

11 A Molecular Understanding of Photochemical Upconverters for Highly Efficient Solar Cells Simon Blacket, Dr David Huang

76 www.physchem2013.com.au 12 High-Throughput, Microfluidic Synthesis of Janus Particles Siobhan Bradley, Prof Thomas Nann, Dr Marta Krasowska

13 A Mechanistic Study into the Destabilization of DNA Triplexes Alex Button

14 Advances and Challenges in High-Level Quantum Chemistry Protocols Dr Bun Chan

15 Incoherent Photon Upconversion and its Applications Yuen Yap Cheng, Andrew Nattestad, Tim F. Schulze , Rowan W. MacQueen , Jens Czolk ,Tony Khoury, Maxwell J. Crossley , Alexander Colsmann ,Klaus Lips , Timothy W. Schmidt

16 Isomer Specific Action Spectra of Retinal Chromophores in the Gas Phase Neville Coughlan, Brian Adamson, Dr Evan Bieske

17 New crown ether core-substituted naphthalene diimide cation sensors Rosalind Cox , Saman Sandanayake , David Scarborough , Ekaterina Izgorodina , Prof Steven Langford, Dr Toby Bell

18 The Role of Spin in Triplet-Triplet Upconversion A.Danos, T.Keevers, Y. Y. Cheng, D. R. McCamey, T. W. Schmidt

19 The Quantum Nature of H2 Bound to Li+–benzene Jordan D’Arcy, Stephen Kolmann, A/Prof Meredith Jordan

20 The multiple structures of vaterite Dr Raffaella Demichelis, Dr Paolo Raiteri, Prof Julian Gale

21 Excited State Localization and Excitation Energy Migration in Multichromophoric Aminoarenes Dr Miroslav Dvorak , Dr Martin Michl, Dr Numan Almonasy , Prof Milos Nepras

22 Alzheimer’s Disease Amyloid-Beta Peptide Interaction with Platinum- based Inhibitors Dr Vidana Epa , Dr Victor Streltsov , Dr Simon James , Dr Vijaya Kenche

23 Does SOMO-HOMO conversion enhance catalysis in radical enzymes? Sarah Faulkner, Michelle Coote , Colin Jackson

24 New Gaussian wave packet methods for chemical dynamics Dr Terry Frankcombe

77 www.physchem2013.com.au

25 A Single Molecule Spectroscopic Evaluation of a Tetra Core- Substituted Naphthalene Diimide Brenton Graystone , Dr Subashani Maniam , Prof Steven Langford , Dr Toby Bell

26 Circularly Polarised Luminescence Spectroscopy of Photosystem II Jeremy Hall , Dr Paul Smith , Dr Rafael Picorel , Prof Elmars Krausz

27 Gas phase photodissociation of N-substituted pyridinium derivatives: electronic spectroscopy and product characterisation Christopher Hansen, Dr Benjamin Kirk, Prof Stephen Blanksby, Dr Adam Trevitt

28 Ultrafast Spectroscopy of Curcumin in Diamide Linked γ-Cyclodextrin Dimers Takaaki Harada, Hamish McTernan, Dr Duc-Truc Pham, Prof Lincoln Stephen, Dr Tak Kee

29 Density Functional Theory and Photo-Ionisation Studies of Gold-Cerium Oxide Clusters Robert A Hardy, Aidan M Karayilan, Gregory F Metha

30 Identification of TCNQF4 Oxidation States via Experimental and Theoretical Vibrational Spectra Dr Naomi Haworth, Dr Chris Thompson, Dr Jinzhen Lu, Nguyen Vo, A/Prof Lisa Martin, Thanh Le, Alan Bond

31 Analysis of conformations and vibrational frequencies of AMP, ADP, and ATP: A combined computational and experimental study Alireza Heidari , Pravindya Haputhanthri , Dr Ekaterina Izgorodina , A/Prof Bayden Wood

32 Imaging Chemical Extraction by Polymer Inclusion Membranes Using Fluorescence Microscopy Dr Clare Henderson, Edward Nagul , A/Prof Trevor Smith, Prof Spas Kolev

33 Investigation of the optical and emission properties of CdSe nanocrystals using defocused widefield microscopy Heather Higginbotham, Dr Tich Lam Nguyen , Dr Alison Funston , Prof Paul Mulvaney, Dr Toby Bell

34 Barriers for Proton Transport in Hydrogen-bound Systems Including Protic Ionic Liquids Dr Jennifer Hodgson, Ahmed Halima, Dr Ekaterina Izgorodina, Prof Douglas MacFarlane

78 www.physchem2013.com.au 35 Experimental and Computational Studies on Bimetallic Clusters of Platinum and Cerium Aidan Karayilan, A/Prof.Gregory Metha

36 Mapping Charge Generation in an Organic Semiconductor using Two- Dimensional Photon Echo Spectroscopy Dr Tak Kee, Yin Song , Dr Yoichi Kobayashi, Dr Ryan Pensack, Prof Gregory Scholes

37 Probing Spin-Dependent Transport and Recombination in Organic Light-Emitting Diodes through Magnetic Resonance Thomas Keevers, Andrew Danos, Dr Karl Weber, Dr Scott Watkins, Dr Dane McCamey

38 Photochemical Studies of Self-Assembled Porphyrin-fullerene Complexes through Transient Absorption Spectroscopy Julie Kho, A/Prof Peter Boyd, Dr Ali Hosseini, A/Prof Cather Simpson

39 How do Bond Dissociation Enthalpies Depend on Protonation State? Michael Morris, Dr Bun Chan, Prof Leo Radom

40 DFT Studies of N2O Reactivity with Vanadium and N-Heterocyclic Carbenes Miranda Shaw, Brian Yates

41 Fourier Transform Infrared Spectroscopic Detection of DNA in Cells Donna Whelan, Dr Keith Bambery, Dr Ljiljana Puskar, Prof Don McNaughton, Ass/Prof Bayden Wood

79 www.physchem2013.com.au Poster Session Two

42 An Impulsive Phase Space Theory for Triple Fragmentation Duncan Andrews, Nicholas Hobday, Mitchell Quinn, Dr Klaas Nauta, A/Prof Meredith Jordan, Prof Scott Kable

43 Calculating the energetics and dynamics of the interaction of molecules with semiconductor surfaces using fragmentation and ab initio calculations: hydrogen atoms and hydrogen-terminated silicon (111) Dr Terry Frankcombe

44 A new way to add hydrogen to aromatics: REMPI studies of benzene+H, toluene+H, naphthalene+H Dr Olha Krechkivska, Dr Klaas Nauta, Prof Scott Kable, Prof Timothy Schmidt

45 Molecular dynamics simulations of the glass transition of water using different intermolecular potentials Cara Kreck, Prof Ricardo Mancera

46 Quasi-Classical Trajectories on a Zero-Point Energy Corrected Potential Energy Surface Kelvin Lee, Stephen Kolmann, Mitchell Quinn, Dr Klaas Nauta, Prof Scott Kable, A/Prof Meredith Jordan

47 New Insights into 1,2,4-trioxolane Stability and the Crucial Role of Ozone in Promoting Polymer Degradation Richmond Lee, Michelle Coote

48 A Kinetic Study of Keto-Enol Tautomerisation of the Medicinal Agent Curcumin with NMR Spectroscopy Mandy Leung, Prof Stephen Lincoln, DrTak Kee

49 Flexible or Rigid? Investigating the Effect of Surface hardness on Anti-Fouling performance Kamron Ley, Dr George Yiapanis , Dr Dave Winkler, Dr Shane Maclaughlin, Dr Evan Evans, Prof Irene Yarovsky

50 Free Energy of Solvation for a Uranium ion in the LiCl-KCl Eutectic Cassandra Lutzko, Maoyan Liu, Angus Gray-Weale

51 Nanostructured Upconverters for Solar Energy Applications Rowan MacQueen, Yuen Yap Cheng, Timothy Schmidt

80 www.physchem2013.com.au 52 In situ High-Resolution Raman Imaging of Erythrocytes from Whole Blood K.M. Marzec, M. De Veij, D. Pérez Guaita, B. R. Wood, S. Chlopicki, M. Baranska

53 Ramps: A new type of basis function for faster quantum chemistry calculations Laura K. McKemmish, Dr Andrew T. Gilbert, Prof Peter M. W. Gill

54 Using 2-Aminopurine to Study Excitation Energy Transfer in DNA Grant McKenzie, Anita C. Jones

55 A new semi-confocal high-resolution FTMW spectrometer Dr Chris Medcraft, Dr Thomas Betz, Dr Melanie Schnell

56 Building Dipole Moment Surfaces with Modified Shepard Interpolation Michael Morris, A/Prof Meredith Jordan

57 Triple-fragmentation of Formaldehyde: using Velocity Map Imaging and 2D REMPI to determine complete photochemical quantum yields Dr Klaas Nauta, Nicholas Hobday, Mitchell Quinn, Gaby de Wit, Duncan Andrews, A/Prof Meredith Jordan, Prof Scott Kable

58 Spectroscopic investigation of boron porphyrin/porphyrinoid complexes Nina Novikova, A/Prof Cather Simpson , Prof Penelope Brothers

59 Jet-Cooled Excitation Spectra of Large Benzannulated Benzyl Radicals: 9- anthracenylmethyl (C15H11) and 1-pyrenylmethyl (C17H11) Gerard O’Connor, Dr George Bacskay, Gabrielle Woodhouse, Dr Tyler Troy, Dr Klaas Nauta, Prof Scott Kable, A/Prof Timothy Schmidt

60 Self-Assembled Nanostructures for High Resolution Characterisation Adabelle Ong, Benjamin Morrison, Clare Henderson, Trevor Smith

61 Product Branching Studies of ortho-Substituted Phenyl + O2 Reactions: Experimental and Theory Matthew B. Prendergast, Benjamin B. Kirk, Stephen J. Blanksby, Gabriel da Silva, Adam J. Trevitt

62 Helium Nanodroplet Isolation Spectroscopy of the Hydroxyl Radical and of its Complexes with Carbon Monoxide and Methane Paul Raston, Tao Liang, Emmanuel Obi, Gary Douberly

81 www.physchem2013.com.au

63 New spin-component scaled MP2 coefficients to approximate CCSD(T) for charged systems Jason Rigby, Dr Ekaterina Izgorodina

64 Permanent Dipole Correlations Drive Self-Assembly in Various Solvents Cameron Ritchie, Dr Angus Gray-Weale

65 Conformational analysis of biomolecules in the gas-phase by optical spectroscopy? Don’t amide if I do Patrick Robertson, Isabella Lobo, Dr Evan Robertson, Dr David Wilson

66 Near-IR Femtosecond Transient Absorption Spectroscopy of Poly(3-hexylthiophene) Nanofibres Charu Rohatgi

67 Electronic Spectroscopy of Cyclic Hydrocarbon Cations in the Gas Phase using Resonance-Enhanced Photodissociation Julian Sanelli, Dr Nahid Chalyavi, Dr Viktoras Dryza, Prof Evan Bieske

68 MCSCF models and competing mechanisms of [4π + 2π] cycloadditions David Scarborough, Christopher Thompson, Ekaterina Izgorodina

69 Photocatalysis of CO2 and H2O using Aun cluster doped TiO2 nanoparticles Kathryn Schroeder, Jason Alvino, Trystan Bennett, Gregory Meth

70 Transient Absorption Spectroscopy of Novel Semiconducting Block Copolymers for Organic Solar Cells Kyra Schwarz, Prof Ken Ghiggino, A/Prof Trevor Smit

71 Phototautomerisation of Carbonyls to Enols at Atmospheric Pressure of N2 Miranda Shaw, Alexander Clubb, Balint Sztaray, David Osborn, Meredith Jordan, Scott Kable

72 Vortex magnetic states in frustrated molecular metal rings: towards single−molecule spin torque effects despite the weak spin−orbit coupling Dr Alessandro Soncini

73 Predicting the outcomes of oxidising processes: The development of a QM/MM hybrid simulation method Dr Matthew Stewart, Prof Harry Ridgway, Prof Stephen Gray, A/Prof Todor Vasiljevic, Prof John Orbell

82 www.physchem2013.com.au 74 Simulation of Energy Transport in Conjugated Polymer Systems Patrick Tapping, Dr Tak Kee, Dr David Huang

75 Distance dependent parallel interactions of graphene with a variety of aromatic molecules Asya Tawfiq, Dr Graham E. Ball, A/Prof John A. Stride

76 Seeing Red: Using Femtosecond Transient Absorption Spectroscopy to Investigate Photodegradation in Anthraquinone Dyes and Pigments Sarah Thompson, Dr Charles Rohde, Dr Erin Griffey, A/Professor Cather Simpson

77 Ligand-mediated control of the surface plasmon resonance in metal nanoparticles generated by laser ablation Rhys Tilbury, Ashley Mulder, Michael Wolter, Dr Massiiliano Massi, Prof Mark Buntine Curtin University

78 Measuring photo-initiated radical chemistry in single microdroplets Bartholomew Vaughn, Phillip Tracey, Dr Adam Trevitt

79 Origin of visible-light activity of fluorinated titanium dioxides: A DFT study Dr Yun Wang, Dr Haimin Zhang, Dr Porun Liu, Prof Huijun Zhao

80 Time-resolved resonance Raman spectroscopy of aryl-diphosphenes Xindi Wang, Jennifer Stott, A/Prof M Cather Simpson

81 Super-Resolution Fluorescence Microscopy for Imaging Virally Induced Changes to the Cell Cytoskeleton Donna Whelan, Aaron Brice, Dr Gregory Moseley, Dr Toby Bell

82 Infrared Spectroscopy of Ethylene Aerosols using Synchrotron Radiation Andy Wong, Prof Don McNaughton, Dr Dominique Appadoo, Ruth Plathe, Dr Evan Robertson, A/Prof Sigurd Bauerecker

83 www.physchem2013.com.au Poster Session 1 binding energies, the docking scores and monitoring the stability of the complexes produced during the MD simulations [4]. The strong electrostatic contribution to the Poster 1 binding energies may be responsible for the higher inhibitory activity Marawan Ahmed, Stefanie Bird, Enzo of the lactone with respect to the Palombo, Kevin Prince, Feng Wang thiolactone series. Preliminary results Swinburne University from this project will be presented at the conference. In silico investigation of inhibiting signaling molecules Keywords for bacterial quorum sensing Quorum Sensing; lactone inhibitors; using molecular modelling Docking; Molecular dynamics

Abstract Treatment of bacterial infections is a major global challenge. It is estimated that bacterial resistance can increase mortality and morbidity by a factor of two [1]. Bacteria continue to develop resistance to current anti-bacterial agents and the problem is becoming more wide-spread [2,3]. The challenge to stop bacterial growing is to inhibit bacterial quorum sensing Figure 1: interaction diagrams for a potential CviR antagonist from the (QS) through the use of small signal lactone series of inhibitors (PDB code: molecule inhibitors. 3QP5).1: 2D ligand

In the present study, the origin of the anti-quorum sensing (QS) activities of several members of a two recently synthesized and in vitro tested classes of lactone (Figure 1) and thiolactone based inhibitors were computationally investigated. Docking and molecular dynamic (MD) simulations and binding free energy calculations of the inhibitors against CviR protein (Figure 2) were carried out to reveal their exact binding and inhibitory profiles. The Figure 2: Three dimensional (3D) ribbon representation for the CviR monomer. higher in vitro inhibitory activity of Solid surface in the LBD represent the the lactone based inhibitors relative exact binding location of the inhibitors. to their thiolactone isosteres was verified based on estimating the 84 www.physchem2013.com.au References and clusters made up of elements [1] S.D. Holmberg, S.L. Solomon, P.A. such as Au or Pt can promote such Blake, Health and economic-impacts reactions by acting as a ‘reservoir’ of antimicrobial resistance, Reviews of for photo-generated electrons. An Infectious Diseases 9 (1987) 1065-1078. important step in understanding the basis for such dramatic [2] S.B. Levy, B. Marshall, Antibacterial increases in catalytic potential is the resistance worldwide: causes, challenges and responses, Nature Medicine 10 (2004) characterisation of these species. 122-129. Given the difficultly associated with acquiring experimental data due [3] A.E. Aiello, E. Larson, Antibacterial to the incredibly small size regime cleaning and hygiene products as of clusters, theoretical chemistry an emerging risk factor for antibiotic can provide an invaluable tool resistance in the community, The Lancet to complement and enhance infectious diseases 3 (2003) 501-506. experimental techniques. [4] M. Ahmed, S. Bird, F. Wang, E. Palombo, In silico investigation of The far infra-red absorption lactone and thiolactone inhibitors in spectra of a series of chemically bacterial quorum sensing using molecular synthesised, atomically precise modeling, International Journal of phosphine-stabilised gold cluster Chemistry (accepted, 08/07/2013). compounds have been recorded using Synchrotron light for the first time. Far-IR spectra of the Au6(Ph2P(CH2)3PPh2)4(NO3)2, Poster 2 Au8(PPh3)8(NO3)2, Au9(PPh3)8(NO3)3, and Pd(PPh3) Jason Alvino, Trystan Bennett, Au6(PPh3)6(NO3)2 clusters reveal a A/Prof Greg Metha complex series of peaks between 80 The University of Adelaide and 475 cm−1, for which all significant peaks can be unambiguously Far-Infrared Absorption assigned by comparison with Spectra of Synthetically- DFT geometry optimisations and frequencies calculations. Strong Prepared Ligated Metal absorptions in all spectra near 420 Clusters with Au6, Au8, Au9 cm−1 are assigned to the P-Ph3 and Au6Pd Metal Cores stretching vibrations. Distinct peaks within the spectrum of each specific Abstract cluster are assigned to the cluster For many years it has been known core vibrations: 80.4 and 84.1 cm-1 that semiconductor surfaces or (Au6) 165.1 and 166.4 cm−1 (Au8), particles such as TiO2 can absorb 170.1 and 185.2 cm−1 (Au9), and light in order to directly drive the 158.9, 195.2, and 206.7 cm−1 (Au6Pd). processes behind industrially relevant chemical reactions including water splitting, CO2 reduction, and many others. It has been shown in recent years that doping TiO2 with various noble metal nanoparticles

85 www.physchem2013.com.au The positions of these peaks are energy density. A catalyst promoting similar to those earlier observed to the selective dehydrogenation of occur for the neutral Au7 cluster in formic acid would permit the use the gas phase (Science, 2008, 321, of formic acid in the transport and 674-676). Au-P stretching vibrations storage of hydrogen. only occur for Au6 near 420 cm-1, although they appear near 180 cm-1 We have been investigating for Au6Pd and involve gold core modifications to zeolites that vibrations. would enable their use as robust and selective catalysts for the decomposition of formic acid to hydrogen and carbon dioxide. Modified zeolites were designed using ab initio calculations, then synthesized and tested to confirm the predictions of the calculations. The results1 show that a germanium catalyst with a sodium counter- Figure 1: Calculated normal mode ion will selectively dehydrogenate displacements associated with the cluster formic acid whereas the protonated core vibrations for Au8 at (a) 165.1 cm-1 zeolite will be selective for and (b) 166.4 cm-1. Phenly groups are dehydration. These results show omitted for clarity. how computational approaches can be elegant and powerful tools in the design of the new catalysts required to answer important and Poster 3 urgent scientific and technological problems. Ruth Amos Australian National University

Catalysis by design: H2- selective formic acid decomposition by zeolites

Abstract One of the major questions of the twenty-first century is how to ensure a sufficient and sustainable supply [1] R. I. J. Amos, F. Heinroth, B. Chan, of energy. Hydrogen fuel cells have S. Zheng, B. S. Haynes, C. J. Easton, A. been proposed as a clean energy F. Masters, T. Maschmeyer, L. Radom, Catalysis by Ab Initio Design: From alternative. However, one major Computational Prediction to the difficulty that needs to be overcome Experimental Demonstration of H2- is finding a viable way to transport Selective Formic Acid Decomposition by H2. Formic acid is a possible medium Na-Ge-ZSM-5, Journal of the American for H2 storage and transport as it Chemical Society (submitted). is not flammable, non-toxic, easily stored and handled, and has a useful 86 www.physchem2013.com.au Poster 4 to the relevant branching ratios. The best studied system is H2CO and the Duncan Andrews, A/Prof Meredith Jordan, results of our PST-roaming theory are Prof Scott Kable compared to experiment in figure The University of Sydney 1. [1, 2] For NO3, the best fit to the experimental data is obtained for A Phase Space Theory for Proam = 0.0075, which is consistent Roaming Reactions with the known geometric constraints to formation of NO + O2. Using this value and the experimental rotational Abstract and vibrational temperatures, we can We describe a new, simple theory accurately model low temperature for predicting the branching fraction experimental branching fractions, a of products in roaming reactions, low temperature NO yield spectrum compared to the analogous and quantum yield data for room barrierless bond dissociation temperature NO3 photolysis, see products. The theory assumes that figure 2. [3, 4] The combination of roaming branches from a barrierless other kinetic theories and the PST- bond dissociation channel at large roaming theory will provide rate inter-fragment separations, where the coefficients for roaming reactions. system is not ergodic. The theory uses a phase space theory (PST) formalism to divide reactive states in the bond dissociation channel into states with enough translational energy to dissociate and states that may roam. Two parameters are required: ΔEroam, the energy difference between the bond dissociation threshold and the roaming threshold, and the roaming probability, Proam, the probability that states that may roam do roam rather than recombine to form reactants. We treat Proam, which is somewhat analogous to the Arrhenius A-factor, as the only adjustable parameter in the PST- roaming theory. The PST-roaming theory is tested against experimental and theoretical data on the Figure 1. Branching fractions for roaming dissociation dynamics of H2CO, NO3 and dissociation predicted by the PST- and CH3CHO. The theory accurately roaming theory (lines) and experimental models the relative roaming to bond values (circles). [1, 2] dissociation branching fraction over the experimental or theoretical energy range available in the literature for each species. ΔEroam is initially fixed to an experimental or theoretical value and Proam is fit 87 www.physchem2013.com.au Poster 5

Simon Ashforth, A/Prof Cather Simpson, Dr Jessica Costa University of Auckland

Femtosecond Laser Parameters Required for Optimal Laser Ablation of Bone

Abstract Femtosecond lasers, which emit high peak intensity laser pulses in the femtosecond range, are currently utilised in industries from cataract surgery to optical technologies. The first investigations of hard biological tissue ablation were conducted in the field of dentistry [1, 2]. However, laser surgery has yet to show wide-scale Figure 2. Quantum yields for room- success in the field of orthopaedics. temperature NO3 photolysis predicted by the PST-roaming theory (bold lines) and Our research investigates the experimental values (symbols and dashed optimum laser parameters required lines). [3, 4] for laser ablation of bone.

References Using a femtosecond laser (pulse [1] Lahankar, S. A.; et al. Chem. Phys. 2008, width = 100fs, repetition rate = 347, 288-299. 1kHz, λ = 800nm), a series of linear cuts and craters were machined in [2] Suits, A. G. Acc. Chem. Res. 2008, 41, freshly harvested bone. By changing 873-881. the peak pulse power applied to the bone sample, we determined [3] Magnotta, F.; Johnston, H. S. Geophys. Res. Lett. 1980, 7, 769-772. the single pulse ablation threshold and relating the diameter of an [4] Orlando, J. J.; et al. J. Phys. Chem. ablated spot to the Gaussian spatial 1993, 97, 10996-11000. distribution of energy [3]. The ablation threshold was found to be 11.21 ± 0.11 Jcm-2 in both ovine and bovine bone tissue indicating that laser ablation of bone tissue is independent of target species.

Further experiments were conducted to determine the relationship between cortical bone removal and the number of incident pulses applied. By altering the laser spot translation rate, we varied the 88 www.physchem2013.com.au number of pulses at each point animal test subjects over a 12 week along the scribed linear cut. Optical time period following femtosecond coherence tomography (OCT) laser bone surgery. and image analysis showed that feature depth is linearly related to the number of pulses applied, irrespective of donor species. Through analysis of these trends, determined that the current minimum cut depth of a single pulse is 0.54µm at a peak pulse fluence of 7.81 Jcm-2, reaching a maximum cut depth of a single pulse of 3.47µm at a peak pulse fluence of 59.79 Jcm-2.

We also investigated the effects of focal depth on ablation rate and found that the optimum depth of focus for maximum ablation occurs when the laser spot is focused below the surface of the bone. OCT and image analysis showed that the Figure 1. Five lines inscribed in bovine optimum depth of focus for maximum cortical bone. The sample was translated past the focal spot at 0.70 μm/step, ablation occurs when the laser spot corresponding to 77 overlapped pulses is focused a 2300 ± 100 µm below at each position, in this example. The the target surface. Comparisons to incident laser pulse parameters: 1 kHz, 800 femtosecond ablation of PMMA and nm, 100 fs, 23.91 J cm-2 pulse fluence. Spot stainless steel showed that maximum beam waist radius = 26.8 μm and is not ablation occurs when the laser spot is varied. focussed between 2000 and 3000 µm below the target surface. References [1] Stern, R.H. and R.F. Sognnaes, Laser Structural analysis of the ablation Beam Effect on Dental Hard Tissues. features using environmental Journal of Dental Research, 1964. 43(5sp): scanning electron microscopy was p. 873-&. performd to assess damaged to the [2] Goldman, L., et al., Impact of the Laser surrounding structure. Femtosecond on Dental Caries. Nature, 1964. 203: p. 417. laser irradiation of bone tissue under our experimental conditions leads [3] Cheng,J.; Liu, C.S.; Shang, S.; Liu, to no signs of thermal shockwave D.; Pierre, W.; Dearden, G.; Watkins, cracking, molten debris deposition K. (2012) “A review of ultrafast laser or charring of the osseous tissue materials micromachining” Optics & Laser whilst leaving hydroxyapatite crystal Technology, 46(0), 88-102 structure intact [4]. [4] Girard, B.; Yu, D.; Armstrong, M.; Wilson, B.; Clokie, C. (2007) “Effects of Finally, preliminary results will be Femtosecond Laser Irradiation on Osseous presented to assess the cellular Tissues” Lasers in Surgery and Medicine, viability and healing ability of live 273-285.

89 www.physchem2013.com.au Poster 6 Poster 7

James Banal, Kenneth Ghiggino, Dr Santiago Barrera Acevedo, Wallace Wong Dr Ekaterina Izgorodina The University of Melbourne Monash University

Twisted Aromatics as Potential Size consistency in Fragment Chromophores for Luminescent Molecular Orbital Approach Solar Concentrators Coupled with Second Order Perturbation Theory (FMO-MP2) Abstract Fluorescence quenching due to Abstract aggregation and small Stokes shift The Fragment Molecular Orbital akin to conventional luminescent (FMO) approach is a computational solar concentrator (LSC) dyes method that can produce accurate – perylenes, coumarins, and ab initio energy calculations of large rhodamines – limits the observed molecular systems with thousands of concentration efficiency of LSC atoms. The FMO approach divides devices from reaching theoretical a system into small fragments and efficiencies. To solve these problems, performs calculations of all individual we propose the use of twisted fragments, as well as, combinations aromatic chromophores as active of two fragments (two-body effect or materials for LSC devices. These FMO2) and three fragments (three- chromophores have atypical body effect or FMO3). The FMO properties such as quantum yield approach can be combined with enhancement upon aggregation different levels of ab initio theory such and large Stokes shift, which are as a second order of perturbation ideal LSC chromophore properties. theory, MP2. The energetic We examined the photophysical contributions of all the fragments properties of different twisted approximate the calculation of the aromatic chromophores for LSC whole system at such level of theory. applications. Both experimental Previously in our group, it was shown and computational results suggest that the three-body effect was that LSCs with pristine twisted necessary to accurately reproduce aromatic chromophore films have the MP2 energies of ionic liquid comparable efficiencies to LSCs clusters, consisting of 4 8 and 16 ions. containing chromophores dispersed The aim of this investigation is to in polymer matrices or based on reduce the number of combinations other state-of-the-art strategies, such of two and three-body fragments as fluorescence resonance energy in the FMO calculation, so that transfer or chromophore alignment computational time and cost are that are designed to circumvent minimised. Therefore, much larger concentration quenching and clusters of ionic liquids (which require parasitic reabsorption problems. more computational time and cost) can also be studied. This hypothesis is based on the fact that in large systems of ionic liquids, the dispersion

90 www.physchem2013.com.au interaction between distant ion Poster 8 pairs (≥ 10 ̊A) can be neglected. Any quantum chemical method Ognjen Belic, Prof Ken Ghiggino, needs to satisfy the size-consistency A/Prof Trevor Smith property to ensure reliable results The University of Melbourne with increasing number of molecules in the simulation. A size-consistent Spatial imaging of method requires that the total fluorescence and photocurrent energy of two non-interacting systems, calculated directly as a in thin film photovoltaics molecular-system, should be the Abstract sum of the energies of the two sub- systems calculated separately. To Photovoltaic cells are an integral part carry out this investigation, clusters in converting nations to carbon-free of ionic liquids of 16, 32 and 64 ion electricity generation. They allow for pairs are considered. The ionic zero-emission energy conversion from liquids are chosen from routinely a natural, and an essentially endless, used combinations of cations, such source – the Sun. Thin-film polymer as C2mim, C2mpyr, N-pyrid and photovoltaic cells, an emerging P2222, and anions, such as BF4, Br, alternative for conventional silicon Cl, DCA and NTF2. The comparison cells, show particular promise in of the results is done with respect to contributing to energy demand the FMO3 calculations including all due to their ease of processing and possible combinations of two and relatively lower manufacturing costs. three-body effects. Calculations However, efficiency issues including are performed using the program optimising active layer morphology GAMESS-US in our group cluster GAIA, currently hinder widespread linked to the Monash Campus Cluster. introduction of this type of solar cell. In this work we describe the development of an instrument for simultaneously monitoring the photocurrent and fluorescence of thin film photovoltaic materials on a microscopic scale. This allows spatial mapping of these important photovoltaic parameters and correlations with blend morphology of the materials can be deduced. The conjugated polymers MEH-PPV, MDMO-PPV and P3HT were blended with PCBM to create photovoltaic devices that were imaged for photocurrent and fluorescence with micron spatial resolution. Our results indicate the impact of film formation conditions on morphology and device characteristics.

91 www.physchem2013.com.au Poster 9 across a wide range of frequencies necessary for detailed investigation, Trystan Bennett, Jason Alvino, in conjunction with the significant and A/Prof Greg Metha unique computational challenges The University of Adelaide presented by these systems.4 In our work we have taken far-IR Far-Infrared Absorption spectra at the IR beamline of the Spectra of Synthetically- Australian Synchrotron, which are presented and elucidated with the Prepared, Ligated Metal assistance of computational Density Clusters with Ru3, Ru4, and Functional Theory based calculations. AuRu3 cores Comparisons are made to previous literature for the Ru3 system,2,3 with Abstract both the low-wavelength Raman Over the past decade there has and IR data discussed. Key metal been great interest shown in the size- core vibrations are identified for all dependent chemical properties of species, and a novel theory for the metal clusters deposited onto active unexpectedly intensity of these key surfaces, particularly with a focus features is presented, wherein it is on catalysis. Most of this work has proposed that the experimental involved the study of size-selected intensity of a given feature depends clusters produced in the gas phase on the atomic motion contribution of and subsequently deposited, or the metal core to that transition. soft-landed, onto appropriately References prepared surfaces. Less common are studies that involve the preparation [1]. Alvino, J.F., Bennett, T., Anderson, of ligand-stabilised metal clusters via D., Donoeva, B., Ovoshchnikov, D., chemical synthesis, immobilisation Adnan, R.H., Appadoo, D., Golovko, V., Andersson, G., Metha, G.F.; Manuscript of these onto a support, and the Submitted, 2013. subsequent activation of the cluster cores by removal of some, or all, of [2]. Kettle, S.F.A., Stanghellini, P.L.; Inorg. the ligands.1 Chem. 1979, 18, 2749-2754.

Infra-red spectroscopy is commonly [3]. Adams, D.M., Taylor, I.D.; J. Chem. Soc. used to observe the vibrational Faraday Trans. 2, 1982, 78, 1561-1571. frequencies of key functional groups [4]. Peng, B., Li, Q-S., Xie, Y., King, R.B., to monitor changes in chemical Schaefer, H.F.; Dalton Trans., 2008, 6977- bonding during chemical synthesis. 6986. Despite this, there have been few studies on ruthenium-based systems which have published detailed infra-red and Raman spectra,2,3 and none that have attempted to computationally identify individual atomic contributions to each spectral feature. This could be due to significant difficulties associated with acquisition of high-quality data

92 www.physchem2013.com.au Poster 10 (a measure of average alignment of dipoles within the liquid). The Quinn Besford, Dr Angus Gray-Weale Kirkwood g-factor is a leading term in The University of Melbourne our model for the g-force.

Our model suggests the strength Thermodynamics of Alcohol of dipole correlation is not linear and Water Binary Mixtures with composition of each polar correlating species. Upon mixing, a Abstract clear correlation is seen between Alcohol and water mixtures have the loss of dipole correlation and long been known to have unusual the size of the alcohol. We see that a mixing thermodynamics, where larger alcohol, such as tert-butanol, the entropy of the system increases destabilises a greater amount of far less than expected for an dipole correlations between water ideal solution of randomly mixed molecules than a smaller alcohol molecules1. Many have argued such as methanol. that this is due to alcohol and water forming clathrate-like structures in The predicted free energy cost the surrounding water. However, from the loss of g-force correlation experiments and simulations have agrees well with experimental failed to convincingly show these thermodynamic data on binary structures2. mixing with water across a range of alcohols and compositions. We investigate these anomalous thermodynamics with respect to We show the g-force resulting from dipole correlation forces in alcohol dipole correlations in a polar liquid and water mixtures. Permanent can account for the anomalous dipole moments in a polar liquid mixing thermodynamics of rotate thermally, and their rotations these polar systems. The g-force become correlated, giving rise to an contribution shows strong agreement attractive dispersion interaction. with the excess free energy of these systems, and the entropic component A polar correlating liquid, such as of the g-force shows the same water, has a dispersion interaction abnormalities as the excess entropy arising from orientational correlations data for these systems, and thus also between the molecules electric agrees with the excess enthalpy. The dipole moments. This results in a g-force has a strong dependence on mean force called the g-force. The the molecular dipole moment, which significance of the g-force has been has shown to be significantly different investigated for single component in the liquid-phase to the gas-phase3. liquids, such as its role in the water’s We choose appropriate dipole hydrophobic effect, but not for moments, but point out that accurate binary liquid mixtures. We develop calculations of the liquid-phase a model for predicting the g-force dipole moments will serve as a good contribution to the thermodynamics test of our theory. Our model involves of mixing for binary systems. Our no other adjustable parameter, and model largely encompasses the static the results suggest the g-force is the dielectric constant of the mixtures dominant force for these mixtures. and the related Kirkwood g-factor 93 www.physchem2013.com.au References yield an emitter in an excited singlet [1] Franks, F, Ives, D, 1966. Quartely reviews, state with approximately twice Chemical Society, 20, 1-44 the triplet energy. The return of the excited emitter to the ground state is [2] Dixit, S, Crain, J, Poon, WCK, Finney, JL, accompanied by the emission of a Soper, AK, 2002. Nature, 416, 829-832 high-energy photon. [3] Silvestrelli, P, Parrinello, M, 1999. Physical Review Letters, 82, 3308-3311 The process of TTA-UC in solution is in part controlled by the diffusion of both emitters and sensitisers in solution. This diffusion influences the time scales and frequency of Poster 11 sensitiser–emitter and emitter–emitter collisions. The relative orientation of Simon Blacket, Dr David Huang emitters during a collision affects their The University of Adelaide electronic coupling, which in turn impacts TTA efficiency. Furthermore, A Molecular Understanding of the efficiency of annihilation has Photochemical Upconverters been shown experimentally to be for Highly Efficient Solar Cells affected by the presence of an external magnetic field. Abstract We use classical molecular dynamics Single-junction solar cells are (MD) simulations to investigate the fundamentally limited by their collisions between emitter molecules. inability to absorb photons with The relative orientation of rubrene energies below the band-gap. and perylene molecules (both However, through the process shown to be effective emitters) of photochemical upconversion during a collision and the influence by triple-triplet annihilation (TTA- of temperature on the time scales UC), sub-band-gap photons can of these collisions are investigated. be converted into higher-energy Results from the MD studies are photons that can potentially be combined with quantum theory to absorbed by the cell. determine the probability of the formation of an emitter in the excited In TTA-UC, a sensitiser molecule singlet state following TTA to give absorbing a low-energy photon a molecular understanding on the undergoes a transition to its efficiency of this process. The results first excited singlet state and are also compared with experiments subsequently crosses to the excited of analogous systems. triplet state. When this sensitiser encounters an emitter molecule in the ground state it may transfer its energy to the emitter, promoting the emitter to a long-lived triplet state. Subsequent collision of two emitters, each in the triplet state, can result in triplet-triplet annihilation (TTA) and potentially

94 www.physchem2013.com.au Poster 12

Siobhan Bradley, Prof Thomas Nann, Dr Marta Krasowska University of South Australia

High-Throughput, Microfluidic Synthesis of Janus Particles

Abstract The synthesis of asymmetric structural units is essential for the bottom up assembly of nanomaterials into superstructures in order to mimic nature. Janus particles – particles with two “faces” - can be considered as one such structural unit. Synthetic methods for creating Janus particles in bulk conditions exist but result in low yields, varied composition or particles that are not uniform in size Figure 2: a) Droplet generation in or geometry. Microfluidics offers the microfluidic device. b) Optical much more controlled reaction micrograph of a pickering emulsion c) Schematic of the produced Janus particle conditions that can be exploited to where quantum dots are attached to one produce high volumes of uniform hemisphere. particles.1,2 This work involves the simple synthesis of Janus particles Literature using a droplet-based microfluidic [1] Zhihong Nie, Jai Il Park , Wei Li , Stefan device. A flow-focusing geometry A. F. Bon and Eugenia Kumacheva. 2008. is integrated into the device to An “Inside-Out” Microfluidic Approach form monodisperse droplets of to Monodisperse Emulsions Stabilized an immiscible liquid containing by Solid Particles. JACS. 130 (49), 16508– homogeneous particles of controlled 16509. wettability. The particles are trapped [2] Rhutesh K. Shah, Jin-Woong Kim and at the droplet interface and the David A Weitz. 2009. Janus Supraparticles surface of the outer hemisphere in by Induced Phase Separation of contact with the continuous phase is Nanoparticles in Droplets. 21, 1949–1953. modified. Finally, quantum dots are attached to this same hemisphere to Acknowledgements create the final, partially fluorescent Australian National Fabrication Facility Janus particles. Such asymmetric (ANFF) particles are characterised using fluorescence spectroscopy, atomic force microscopy (AFM), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and transmission electron microscopy (TEM).

95 www.physchem2013.com.au Poster 13 experiments. The destabilisation of DNA triplexes by two known Alex Button polyamide triplex destabilisers, The University of Adelaide Netropsin & Diminazene, as well as a series of N-methyl pyrrole analogues A Mechanistic Study into the of Netropsin, was investigated experimentally & by simulation Destabilization of DNA Triplexes to elucidate the molecular-level Abstract mechanism of triplex destabilisation. Friedreich’s ataxia (FDRA) is a neurodegenerative disorder and the most common of the axtaxia’s (affecting 1 in 50,000). The disorder Poster 14 is caused by the formation of a triple-stranded DNA triplex about Dr Bun Chan an expanded GAA repeat tract The University of Sydney sequence in the genome. The presence of this DNA triplex causes Advances and Challenges an inhibition of the neighbouring FXN in High- Level Quantum gene, which results in the symptoms Chemistry Protocols of FRDA. Recent in vivo studies have shown that destabilization of the Abstract DNA triplex causes an increased Computational chemistry is activity of the FXN gene and thus nowadays an indispensable tool it is hypothesised that therapeutic to chemists. In particular, the destabilization of the DNA triplex emergence of quantum chemistry could provide an effective treatment composite protocols has enabled for FDRA. Short polyamides provide highly accurate prediction of an attractive candidate for thermochemical properties for a therapeutic destabilization due to wide range of small to medium-sized their low toxicity and high relative cell species. These methods generally permeability. provide excellent approximations to a high-level procedure by DNA triplexes containing a 5 GAA a combination of lower-level repeat tract were produced from methods, at a substantially reduced free oligomers. These triplex structures computational cost. Further were simulating using an atomistic development of these procedures will model and were compared to enable accurate computations for experimental results obtained by larger systems that are beyond the ion-mobility mass spectrometry. reach of current methodologies, and The theoretical and experimental improve the accuracy for systems collisional cross-sections were that represent significant difficulties compared as a means of confirming even for the latest protocols. In the accuracy of the simulations. The this presentation, a synopsis on our DNA triplexes were characterised development of composite methods by ion-mobility mass spectrometry will be given, together with an as well as by UV-Vis melting spectra overview on challenges that remain fluorescent gel electrophoresis to be overcome. 96 www.physchem2013.com.au [1] Chan, B.; Karton, A.; Raghavachari, K.; light, red to green, red to blue and Radom, L. J. Chem. Theory Comput. 2012, from green to blue light. The red to 8, 3159. yellow upconversion achieved a TTA efficiency of 33%1 with a theoretical [2] Chan, B.; Radom, L. J. Chem. Theory Comput. 2012, 8, 4259. limit of 60%2; the highest reported yield and surpasses the previously assumed 11.1% limit. This red to yellow UC system has been shown capable of assisting the sub-bandgap light Poster 15 harvesting of amorphous silicon solar cells3, organic cells4 and dye- Yuen Yap Cheng1, Andrew Nattestad2, Tim sensitized solar cells (DSC)5. F. Schulze3, Rowan W. MacQueen1, Jens Czolk4 ,Tony Khoury1, Maxwell J. Crossley1, Alexander Colsmann4 ,Klaus Lips3, Timothy W. Schmidt1

1. The University of Sydney, 2. The University of Wollongong, 3. Institute for Silicon Photovoltaics, Helmholtz-Zentrum Berlin, Germany, 4. Karlsruhe Institute of Technology, Germany

Incoherent Photon Upconversion and its Figure 1: Enhanced DSC incident photon- Applications to-current conversion efficiency (IPCE) has been observed with activated UC system Abstract under sub-bandgap illumination. Incoherent photon upconversion (UC) via triplet-triplet annihilation (TTA) is 1. YY Cheng, T Khoury, RGCR Clady, M a potential photochemical process Tayebjee, NJ Ekins-Daukes, MJ Crossley to assist semi-conductors towards and TW Schmidt, Physical Chemistry efficient use of the solar spectrum Chemical Physics, 2010, 12, 66 for photoelectric conversion and 2. YY Cheng, B Fückel, M Tayebjee, T water splitting. This system comprises Khoury, RGCR Clady, NJ Ekins-Daukes, of a sensitizer-emitter mixture: the MJ Crossley and TW Schmidt, Journal of Physical Chemistry Letters, 2010, 1, 1795 sensitizer molecules absorb low energy photons (hν1) and store 3. YY Cheng, B Fückel, RW MacQueen, the energy in their long-lived first T Khoury, RGCR Clady, TF Schulze, NJ Ekins-Daukes, MJ Crossley, B Stannowski, K excited triplet state (T1). Each emitter Lips, TW Schmidt, Energy & Environmental molecule quenches the energy Science, 2012, 5, 6953-6959 from one T1 sensitizer, followed by TTA among T1 emitters to generate 4. TF Schulze, J Czolk, YY Cheng, B Fückel, RW MacQueen, T Khoury, MJ Crossley, B one excited singlet emitter (S1) and Stannowski, K Lips, U Lemmer, A Colsmann, one ground state emitter (S0). The TW Schmidt, The Journal of Physical S1 emitter then fluoresces a higher Chemistry C, 2012, 116, 22794-22801 energy photon (hν2) to return to 5. A Nattestad, YY Cheng, RW MacQueen, its ground state. We have shown TF Schulze, FW Thompson, AJ Mozer, B upconversion from red to yellow Fückel, T Khoury. 97 www.physchem2013.com.au Poster 16 ion packets are irradiated with tuneable laser light at the entrance Neville Coughlan, Brian Adamson, of the drift region. Absorption of a Dr Evan Bieske photon induces photo-isomerization The University of Melbourne or photo-dissociation of the ions, altering their conformation and Isomer Specific Action Spectra consequently their drift speed. of Retinal Chromophores in the These processes are observed by comparing ions’ arrival time Gas Phase distributions (ATD) with the laser off and with the laser on. It is evident Abstract several isomers of retinal and the This poster describes the behaviour Schiff bases exist in the gas state of gas-phase molecular ions as indicated by their ATDs (Fig. 1). undergoing photo-isomerization Density functional theory (DFT) and photo-dissociation in a custom- calculations are implemented to built ion mobility spectrometer. The complement the experimental target molecules are protonated data. Geometries and vibrational Schiff bases of retinal. Retinal is the frequencies are calculated at the light-sensitive molecule that triggers M062X/6-311G(2d,2p) level to map the chemical cascade underpinning the ground state potential energy human vision. Photo-isomerization surface. TD-DFT calculations are is the fundamental event that alters used to model the first excited the quaternary conformation of state potential energy surface. Rhodopsin, signalling absorption of Ion mobilities are predicted using light. Lysine and butylamine Schiff MOBCAL, using the calculated bases of retinal have been prepared geometries and charge distributions. to model the immediate biological environment of the chromophore. We [N-retinylidene-n-butylamine + H]+ aim to collect photo-isomerization [N-retinylidene-n-butylamine + H]+ action spectra of these species by [N-retinylidene-n-butylamine + H]+ measuring the photo-response as a function of laser wavelength. The References experimental approach is based [1] B. D. Adamson, N. J. A. Coughlan, R. E. on an ion mobility spectrometer, Continetti, and E. J. Bieske. Phys. Chem. with the provision for optical access Chem. Phys., 2013, 15, 9540-9548. to drifting ions. Electrosprayed ions are periodically injected into [2] U. F. Röhrig, L. Guidoni, and U. the drift region, and travel under Rothlisberger. Biochemistry, 2002, 41, the influence of an electric field 10799–10809. through nitrogen buffer gas towards [3] S. Sekharan and K. Morokuma. J. Am. a detector. The drift speed of the Chem. Soc., 2011, 133, 19052–19055. charged molecules depends on their collision cross section and therefore, [4] M. F. Mesleh, J. M. Hunter, A. A. their conformation. Because the Shvartsburg, G. C. Schatz and M. F. ions are mass selected, isomers of Jarrold, J. Phys. Chem. A, 1997, 101, 968. each species with the same m/z are resolved. To measure a photo- isomerization action spectrum the 98 www.physchem2013.com.au through fluorescence readouts.1 Chemosensors for targeting cations have been of interest over many years due to their importance in biological processes.2 Crown ethers are well established as effective binding sites for cations. They have the advantage of being selective towards different cation targets by altering the size and nature of the crown. Core substituted naphthalene diimides (cNDIs) are a new class of chromophore with attractive optical properties such as tunable absorption and emission properties depending on the nature and number of the core substituents and are ideally suited for forming the basis of new chemosensing molecular systems.3 Fig. 1: ATDs of electrosprayed ions (left, grey = C, blue = N, hydrogens omitted for clarity) drifting in nitrogen buffer gas: laser We recently developed two off (right, top); difference between laser cNDI systems capable of on (532 nm Nd/YAG) and laser off ATDs sensing protons via optical and (right, bottom) fluorescent readouts.4,5 The ease of functionalising cNDIs has led to the exploration of cNDIs as other potential sensors. By changing the nature of the substituent to Poster 17 different sized crown ethers, specific cations can be targeted. Two new Rosalind Cox, Saman Sandanayake, David Scarborough, Ekaterina Izgorodina, cNDI based chemosensors 1 and Prof Steven Langford, Dr Toby Bell 2, that incorporate a crown ether Monash University binding site directly have now been synthesised and their physical New crown ether core- properties investigated. Here we show that altering the size of the substituted naphthalene crown ether not only changed the diimide cation sensors target analyte, but also affected the sensing mechanism of the Abstract chemosensor. Chemosensors are compounds which give a strong optical readout, such Compound 2 showed selective as a colour change in the UV-visible binding towards K+ and Na+, giving a region or in fluorescence output, response in the UV-Visible absorption on binding with a target analyte. spectra. Within 1 equivalent of the This allows for real-time and real- target cation, the absorbance blue space sensing of the analyte as well shifted 75 nm (Fig 1b) providing a as providing high sensitivity and a clear optical readout of the presence rapid response time, particularly of K+ or Na+. Compound 1, which 99 www.physchem2013.com.au incorporates a slightly smaller crown, was shown to be selective to Ca2+, showed an increase in fluorescence output, but only minimal changes in its UV-Visible spectrum. Furthermore, 1 requires many times excess to fully restore fluorescence.

Computational studies were performed on 1 and 2 to investigate the binding mechanisms involved. For 2, insertion of the cation is directly into the crown ether, where it coordinates to the oxygen atoms in the crown. This causes the crown to twist out of plane relative to the rest of the molecule, inhibiting electron donation from the lone pair from the tertiary nitrogen to the NDI core. This creates the significant colour change observed in the UV-Vis absorption Figure 1. a) Structure of crown ether based spectra. For 1, however, the target SANDIs. b) UV-Vis absorption spectra of analyte, Ca2+, does not sit in the 2 in EtOH, and with successive additions crown, but rather coordinates to both of 0.125equivalents of KCl up to 1.0 the crown ether oxygens and the equivalents. oxygen of the imide.

[1] Callan, J. F.; de Silva, A. P; Magri, D. C. Tetrahedron, 2005, 61, 8551. Poster 18 [2] He, H.; Mortellaro, M.; Leiner, M. J. P.; Fraatz, R. J.;Tusa, J. J. Am. Chem. Soc. A.Danos, T.Keevers, Y. Y. Cheng, 2003, 125, 1468. D. R. McCamey, T. W. Schmidt The University of Sydney [3] Sakai, N.; Mareda, J.; Vauthey, E.; Matile S. Chem. Commun., 2010, 46, 4225. The Role of Spin in Triplet-Triplet [4] Cox, R. P.; Higginbotham, H. F.; Upconversion Graystone, B. A.; Sandanayake, S.; Langford, S. J.; Bell, T. D. M. Chem. Phys. Abstract Lett., 2012, 521, 59. Triplet-Triplet Annihilation (TTA) [5] Higginbotham, H. F.; Cox, R. P.; Upconversion is a class of Sandanayake, S.; Graystone, B. A.; photochemical reactions that Langford, S. J.; Bell, T. D. M. Chem. combine the energies of two Commun., 2013, 49, 5061. incoherent photons into one of higher energy. Liquid upconverting mixtures are being investigated as a way to enhance solar electricity generation: using these devices, wavelengths of sunlight with 100 www.physchem2013.com.au energy below the bandgap of a contribute to the singlet product or semiconductor photovoltaic device, quench triplet energy, whether spin which are normally not absorbed, orientations are preserved in non- can be reclaimed and converted annihilating collisions, and explaining into electricity. Peak enhancements reported non-uniform effects of static of the external quantum efficiency magnetic fields on upconversion of over 2% have been reported intensity. and work continues to increase this enhancement further. In the absence of applied magnetic fields, we expect nuclear coupling to The upconversion process begins align electron spin with an axis of the when sensitiser molecules absorb excited molecules. In this case, the low energy photons and generate formation probabilities of the different triplet excited states in other emitter multiplicity annihilation products molecules. An annihilation event depend on the relative orientations allows two excited emitter molecules of the colliding molecules. Molecular to disproportionate their energy, dynamics simulations of our producing one higher energy excited upconverting mixtures are used to singlet and one ground state singlet. determine average collision rates Fluorescence from the highly excited and orientations, which can then singlet produces the upconverted be compared to experimental photon. upconversion rate constants.

Fundamental aspects of the spin mixing process that controls annihilation remain poorly understood. Our aim is to develop Poster 19 a quantum mechanical description Jordan D’Arcy, Stephen Kolmann, of the annihilation event, which can A/Prof Meredith Jordan predict the formation probabilities The University of Sydney of the different multiplicity products, and improve upon kinetic models The Quantum Nature of H2 which currently dominate this field. Bound to Li+–benzene Electron Paramagnetic Resonance Abstract (EPR) is an ideal tool for examining the role of triplet spin in TTA upconversion. Microporous materials such as metal- Following Zeeman splitting by organic frameworks (MOFs) are under a magnetic field, microwave or investigation as potential H2 storage radiofrequency radiation can be materials. As the lightest molecule, used to manipulate the populations H2 exhibits quantum-mechanical of the triplet spin states. Simultaneous behaviours at low temperatures, measurement of the upconversion such as the delocalisation of its intensity reveals changes in the nuclear wave function. The effect formation rate of the singlet product. of this behaviour on the interaction Of particular interest to us are: between H2 and microporous the low field spin populations of storage materials remains largely molecules in solution, identifying unexplored, and computational which triplet pair configurations simulations of H2 uptake typically 101 www.physchem2013.com.au treat H2 as a classical point particle. Through a better understanding of (H2)n¬–Li+–benzene (n = 1–3)[1] is a the way H2 interacts with microporous model system for H2 adsorbed to a frameworks, materials with improved Li-doped MOF or similar material. The H2 storage capacities can be small size of the system facilitates the designed. fully coupled, anharmonic quantum treatment of H2, using the rigid-body approximation. In previous work, we performed rigid-body quantum diffusion Monte Carlo (RB-DMC) simulations on H2–Li+–benzene, and found that zero-point energy accounted for 35% of the 19.0 kJ mol-1 binding energy, resulting in the delocalisation of H2 above the Li+–benzene system. [2] Here, we extend the study to (H2)2–Li+– benzene. RB-DMC simulations were performed on a potential-energy surface interpolated from M05-2X/6- 311+G(2df,p) electronic structure calculations. We found that the addition of a second H2 to Li+– benzene was insufficient to localise the H2 nuclear wave function, and both H2 remained delocalised above the system. Zero-point energy was almost 45% of the 13.3 kJ mol-1 Figure 1. The (H2)2–Li+–benzene model electronic binding energy, indicating system. Hydrogen atoms are white, carbon atoms black and Li+ pink. that the quantum nature of H2 cannot be ignored in these weakly [1] Kolmann, S. J.; Chan, B.; Jordan, M. J. bound systems. Furthermore, we Chem. Phys. Lett. 2008, 467, 126–130. performed RB-DMC simulations on a fragment potential for (H2)2–Li+– [2] Kolmann, S. J.; D’Arcy, J. H.; Jordan, benzene, reducing computational M. J. J. Chem. Phys. 2013, submitted for expense with no loss in accuracy. The publication. fragment potential-energy surface will be applied to (H2)3–Li+–benzene, as well as larger RB-DMC and path- integral simulations with periodic boundary conditions. With periodic boundary conditions, the (H2)n¬–Li+– benzene system is extended in three dimensions, forming a more realistic representation of a microporous H2 storage material. Bulk H2 uptake characteristics will be predicted over a range of temperatures, without neglecting quantum behaviour. 102 www.physchem2013.com.au Poster 20 direction for future investigation that may influence which of the possible Dr Raffaella Demichelis, Dr Paolo Raiteri, vaterite structure is obtained. Prof Julian Gale Curtin University More generally, a wide variety of structures exhibiting minor structural The multiple structures of and energetic differences might exist vaterite in nature, as a result of nucleation in different environments and at Abstract different conditions, which might promote the formation of a particular Vaterite (CaCO3) is a metastable stacking sequence or chirality. polymorph that plays a fundamental role in the nucleation and crystal growth of calcium carbonate under biogenic conditions. In particular, the nucleation of vaterite Poster 21 is often observed from amorphous calcium carbonate precursors, with Dr Miroslav Dvorak 1, Dr Martin Michl 2, 3 3 biomolecules acting as structural Dr Numan Almonasy , Prof Milos Nepras stabilisers. 1. The University of Sydney, 2. Czech Technical University in Prague, Despite the role of vaterite in 3. University of Pardubice biomineralization, the nature of its disordered structure has been object of intense debated for a long time, Excited State Localization and with various authors suggesting Excitation Energy Migration apparently conflicting models. in Multichromophoric Through first principle simulation, a Aminoarenes link between the most recent models proposed in the literature has been Abstract established. Aminoaryl derivatives connected to 1,3,5- triazine ring have been The new model, consisting of multiple used as molecular building structures, is supported by recent blocks for preparation of a experimental evidences showing that manifold of multichromophoric vaterite crystallises with “at least” compounds. Specifically, dyads two different structures. The disorder with 1-aminopyrene as a donor of vaterite is here interpreted in and 3-aminobenzanthrone or terms of different orientations of the 3-aminoperylene as an acceptor carbonate anions, different stacking of electronic excitation energy and sequences of the carbonate layers, multichromophoric compounds with and possible chiral forms. Hence, different number of aminopyrene vaterite should be considered as or aminoanthracene moieties were a combination of different forms prepared in order to study electronic exhibiting similar average properties, excitation energy transfer and rather than a single “disordered” localization of excited states [1, 2]. structure. Furthermore, chirality represents a new and important

103 www.physchem2013.com.au The fluorescence anisotropy aminoaryl substituent and are measurements of two sets predominantly localized on the of molecules containing individual chromophores. different number (one, two or three) of 1-aminopyrene or We interpret the photophysical 2-aminoanthracene chromophores behavior of these types of attached to the central triazine ring multichromophores in terms of were used to investigate excitation excitation energy migration, energy migration. The fluorescence which causes depolarization of anisotropy has similar features for fluorescence in the case of higher both sets of compounds: In the energy excitation, and direct case of single 1-aminopyrene population of localized excited state chromophore, it has almost constant in the case of excitation to the red value near 0.3 over the lowest edge of the absorption band. absorption band. On the other hand, the anisotropy increases [1] El-Sedik et al., Dyes and Pigments 92 3 with wavelength from much lower (2 012), 1126 -1131 value ~ 0.1 at the blue edge and [2] N. Almonasy et al., Dyes and Pigments approaches the value of ~ 0.3 at the 82 3 (2009), 416-421 red edge of the peak in the case of [3] M. Dvorak et al., Journal of molecules containing two or three Fluorescence 21 3 (2011), 971-974 chromophores [3]. Similar holds for 2-aminoanthracene derivatives. The presence of additional aminoanthracene chromophores results into decrease of the Poster 22 fluorescence anisotropy value across Dr Vidana Epa 1, Dr Victor Streltsov 1, the region 320-400 nm compared to 1 2 the molecule bearing only the single Dr Simon James , Dr Vijaya Kenche aminoanthracene. This decrease 1. CSIRO Materials Science & Engineering, is pronounced with the increasing 2. Florey Institute of Mental Health number of the chromophores. But, at the very red edge of the spectra, Alzheimer’s Disease Amyloid- the fluorescence anisotropy reaches almost the same value of about 0.3 Beta Peptide Interaction with for all three compounds. Platinum-based Inhibitors

Quantum chemical methods were Abstract used for calculation of excited states Alzheimer’s disease (AD) is a properties of the above mentioned progressive neurodegenerative compounds. The calculations disorder causing the most common indicate the presence of pairs or form of dementia in humans. The triplets of excited singlet states pathology of AD is characterised in compounds with two or three by large extracellular plaques in identical aryl-amino substituents, the brain. The major component of respectively. The excited states in these plaques is the 39-43 amino acid these pairs and triplets have similar residue amyloid beta (Aβ) peptide. nature as two lowest excited states Binding of metal ions such as Cu, Fe, of the compounds with only single and Zn to Aβ not only enhances its 104 www.physchem2013.com.au aggregation, but also, in the case of neutral delocalised radicals can Cu and Fe, leads to the production of be stabilized significantly by remote reactive oxygen species (ROS) in the negative charges, even in the presence of reducing agents such absence of permanent dipoles. as ascorbate. Anti-AD therapeutic This electrostatic stabilizing effect design has focussed both on the occurs because the delocalised inhibition of production of Aβ as well electrons of the radical interact less as on the inhibition of aggregation of strongly with the negative charge Aβ. Recently it has been shown that than the radical’s positive nuclei, Pt(II)-1,10-phenanthroline compounds resulting in a net lowering in the bind to Aβ, inhibit the Aβ aggregation system’s energy and in particular, and generation of ROS, and ablate the energy of the SOMO. This SOMO the Aβ-induced neurotoxicity. stabilization is so pronounced that Knowledge of the atomic structure it drops lower in energy than some of the complexes made by these Pt of the radical’s fully occupied compounds with Aβ would greatly orbitals, in direct violation of the facilitate therapeutic development. Aufbau principle; an effect known In this work, we combined density as ‘SOMO-HOMO conversion’. The functional theory modelling with stabilization is more pronounced with X-ray absorption spectroscopy and a more delocalised radical and a mass spectrometry experiments more localised negative charge, the to derive structural models of the latter corresponding to an unstable interaction of these Pt compounds anion in real systems. This effect has with A. currently been observed only in the gas phase and non-polar solvents, where the anion is free from the stabilizing effects that are provided by a polar solvent. However, the Poster 23 active site of an enzyme is a highly controlled environment which is Sarah Faulkner 1, Michelle Coote 2, Colin Jackson 1 often isolated from the solvent; this is particularly true of enzymes 1. Australian National University, 2. ARC which generate radicals during Centre of Excellence for Free-Radical catalysis, as they must protect the Chemistry and Biotechnology, Research, radical long enough for the desired reaction to occur. SOMO-HOMO Does SOMO-HOMO conversion conversion could enhance enzyme enhance catalysis in radical catalysis in two ways; by stabilizing the transition state of a reaction more enzymes? than the enzyme-reactant complex, Abstract or by stabilizing a product radical, making the overall reaction more In the absence of direct conjugation, thermodynamically favourable. remote substituent effects on radical Following investigation of a wide stability are generally thought to range of radical enzymes, a member decay rapidly with distance and of the radical SAM superfamily has become insignificant beyond a few been found which appears to Angstroms’ separation. However, recently it has been shown that 105 www.physchem2013.com.au provide an excellent environment effort that scales exponentially for SOMO-HOMO conversion. Its with the system size. Methods active site is largely hydrophobic and based on Gaussian wave packets becomes sealed from solvent when (GWPs) present an alternative its substrate binds. In this hydrophobic to the grid-based approaches, site are several aspartate residues offering advantages such as which are predicted to have better scaling to large numbers unusually high pKA’s, a feature that is of degrees of freedom and much unexplained by the current literature. more achievable requirements for It also forms a highly stable protein potential energy surface evaluation. radical during its catalysis. In order to However, contemporary GWP-based test whether this enzyme uses SOMO- approaches such as full multiple HOMO conversion to assist radical spawning and the variational formation, these unusually unstable multiconfigurational Gaussian aspartates are being mutated to method are not effective when asparagine; a residue with similar applied to many types of reactions. hydrogen bonding properties and shape, but unable to form an anion. We have recently developed a new The reaction rates of these mutant GWP-based method incorporating enzymes, along with predictions several key innovations. The Basis from QM/MM modelling and DFT Expansion Leap multiconfigurational calculations on small model systems Gaussian (BEL-MCG) method uses of the wild type and mutant active Gaussian functions simply as a sites, will be used to determine flexible, redundant basis set. Basis whether SOMO-HOMO conversion function motion is completely in the transition state or product removed from the physics of the enhances the enzyme’s catalysis. system, dramatically reducing the number of equations of motion required. This method allows accurate propagation of the quantum wave packet describing Poster 24 molecular nuclei, giving accurate reaction probabilities on any Dr Terry Frankcombe Australian National University reasonable molecular potential energy surface. The Schrödinger equation is solved to a pre-specified New Gaussian wave packet level of accuracy, meaning all methods for chemical quantum effects are reproduced. dynamics Similar methodology can be used to calculate the rovibrational ground Abstract state wave function of a system, Quantum dynamics calculations in allowing the rapid calculation of molecular scattering are demanding. zero point energies without reference Even after 40 years of development, to presumed functional forms or the state of the art for accurate harmonic/anharmonic character. In scattering simulations is simulating this talk the BEL-MCG approach shall reactions in five atom systems. Grid- be described and demonstrated based methods dominate the field, with simple and multi-dimensional despite requiring computational examples. 106 www.physchem2013.com.au Poster 25 search for more is ongoing.

Brenton Graystone, Dr Subashani Maniam, Substituted amino naphthalene Prof Steven Langford, Dr Toby Bell diimides (SANDIs) show promise in Monash University SMFM applications, as they generally possess high quantum yields (Φf~0.5), A Single Molecule long fluorescence lifetimes (τf~10 Spectroscopic Evaluation ns) and are photostable under SMFM conditions.2,3,4 However, a of a Tetra Core-Substituted drawback of these fluorophores is Naphthalene Diimide their low molar absorptivity (εr~8- 20000 mol-1cm-1L).2,3,4 We have Abstract recently developed a deep red- Since the first reported observation emitting SANDI 1 (λmax = 666 nm) of single molecules at room which shows promise in addressing temperature using fluorescence this drawback (Fig. 1). The molar microscopy, the use of single absorptivity is greatly improved molecule fluorescence microscopy (εr~72000 mol-1cm-1L), and although (SMFM) techniques, particularly in there is some trade off in quantum biophysics, has rapidly expanded.1,2 yield (Φf~0.17), 1 is ca. 3 times brighter With this expansion, dyes that absorb than simple mono- and di-substituted and emit in the red region of the SANDIs in the literature.4 electromagnetic spectrum have become highly sought after. This is due to the decreased background absorption and emission observed when imaging biological materials in this region, the so-called biological ‘window of transparency’.2 The advantage of SMFM techniques is that detailed information, often lost to ensemble averaging, is revealed.2 As a result a better understanding of the various behaviours that make up the properties of the bulk sample are Figure 1: a) Structure of 1; b) Photon trajectory; c) intensity map of single obtained. molecules of 1.

A chromophore for use in SMFM Single molecules of 1 in PMMA films techniques must meet specific show that the intensity of emission, requirements: large molar absorption fluorescence lifetime and emission coefficients, εr, high fluorescence maxima did not vary significantly over quantum yields, Φf, and high time, or from molecule to molecule. photostability - being capable of at Many molecules were exceptionally least 106 absorption-emission cycles long-lived, undergoing hundreds prior to irreversible photobleaching. of millions of excitation-emission Long fluorescence lifetimes in the cycles before photobleaching. Thus nanosecond range are also useful. 1 appears ideally suited to single There are few red emitting dyes that molecule labelling applications. meet these requirements and the 107 www.physchem2013.com.au References generated as a waste product. [1] Betzig, E.; Chichester, R. J. Science The main electron-transfer cofactors 1993, 262, 1422-1425. of PSII are known from various spectroscopies, confirmed by x-ray [2] Bell, T. D. M.; Yap, S.; Jani, C. H.; crystallography. However unresolved Bhosale, S. V.; Hofkens, J.; De Schryver, F. questions remain regarding kinetics C.; Langford, S. J.; Ghiggino, K. P. Chem. – and mechanisms in the enzyme.1 Asian J. 2009, 4, 1504-1508. The antenna chlorophylls are [3] Bhosale, S. V.; Jani, C. H.; Langford, S. J. well separated from the reaction Chem. Soc. Rev. 2008, 37, 331-342. centre, and the question of whether the rate-limiting step is excitation [4] Sakai, N.; Mareda, J.; Vauthey, E.; energy transfer or electron transfer Matille, S. Chem. Commun. 2010, 46, 4225- remains a controversial topic. 4237. One key method in understanding the dynamics of PSII is the use of multi-dimensional computational analysis to model spectroscopic Poster 26 results such as absorption, circular dichroism, fluorescence, and others Jeremy Hall 1, Dr Paul Smith 1, Dr Rafael in terms of the crystal structure, in Picorel 2, Prof Elmars Krausz 1 parallel. So far, different studies have successfully accounted for different 1.Australian National University, sets of spectroscopies but strong 2. CSIC, Zaragoza, Spain disagreement between these studies suggests that the true solution is some Circularly Polarised way off.2 Luminescence Spectroscopy of Photosystem II Circularly polarised luminescence (CPL, the difference between left- Abstract and right-circularly polarised light in emission) is one technique that has Photosystem II (PSII) is the enzyme not yet been brought to bear on this that performs the initial reactions of challenging problem. Optical activity oxygenic photosynthesis, including in light harvesting proteins arises from water splitting and formation of exciton coupling between chlorophyll oxygen gas. This multi-protein molecules that are packed in chiral complex contains two light- arrangements. This coupling is harvesting antenna proteins, CP43 relatively easily determined by the and CP47, connected on either distances and orientation of the side to the reaction centre (RC). chlorophyll transition dipoles involved. Chlorophyll molecules bound at The CPL of exciton states matches specific locations in the antennas their circular dichroism. Rather than absorb light energy and transfer it to making CPL redundant, this fact is chlorophylls in the RC. Excitation of useful for identifying the fluorescing the RC initiates a series of electron- exciton states in PSII, as fast excitation transfer reactions who’s final result energy transfer to the lowest excited is the reduction of a plastoquinone state cannot be taken for granted. molecule using electrons extracted CPL results can therefore provide an from H2O, with oxygen gas additional constraint for structure- 108 www.physchem2013.com.au based calculations of PSII dynamics. Poster 28 Many challenges arose in measuring the polarisation of emission from Takaaki Harada, Hamish McTernan, Dr fragile protein complexes at Duc-Truc Pham, Prof Lincoln Stephen, Dr temperatures down to 5 K. With Tak Kee accuracy of circular polarisation of The University of Adelaide 1 part in 104 required, polarisation artifacts were particularly Ultrafast Spectroscopy of troublesome. Artifact-free circular Curcumin in Diamide Linked polarisation of luminescence from PSII core complexes and the isolated γ-Cyclodextrin Dimers proximal antennas CP43 and CP47 Abstract have now been obtained providing further insights into this important Curcumin is a biologically active enzyme. polyphenol extracted from turmeric. Poor aqueous stability and solubility of curcumin have thus far hindered the development of curcumin as a drug. Cyclodextrins (CDs) have been suggested as drug delivery agents for curcumin owing to their non-toxic nature. Our previous study showed that diamide linked γ-CD dimers, namely 66γCD2su or 66γCD2ur, are able to stabilize curcumin at a greater extent than single CDs through a cooperative 1:1 host guest complexation. We have proposed that the high stability of curcumin may be attributed to exclusion of water molecules in 66γCD2su and Figure 1. (a) PD action spectrum monitoring the methane (CH4) loss 66γCD2ur. However, fluorescence channel from the UV photolysis of spectroscopic results suggest that N-methylpyridinium. (b) Simulated there are still some interactions N-methylpyridinium UV absorption between curcumin and water in spectrum. 66γCD2su and 66γCD2ur. In this study, we aim to use ultrafast spectroscopy [1] C. S. Hansen, B. B. Kirk, S. J. Blanksby, to understand the water-curcumin R. A. J. O’Hair and A. J. Trevitt, J. Am. Soc. interactions on the time scales of Mass Spectrom, 24(932) 2013. 100 femtoseconds (fs, 10-15 s) and [2] A. T. Maccarone, B. B. Kirk, C. S. picoseconds (ps, 10-12 s). Ultrafast Hansen, T. M. Griffiths, S. Olsen, A. J. Trevitt, excited state dynamics of curcumin S. J. Blanksby, J. Am. Chem. Soc, 135(9010) in 66γCD2su and 66γCD2ur will be 2013. presented in comparison to curcumin in methanol. When free curcumin is present in methanol, the excited state is deactivated through fluorescence, solvation, solvent-mediated excited state intramolecular hydrogen 109 www.physchem2013.com.au transfer (ESIHT), giving rise to an potential of cerium oxide which excited lifetime of ~200 ps. The allows surface oxygen atoms to be solvent-mediated ESIHT is an efficient readily abstracted by adsorbed gas relaxation pathway due to a phase reactants. The adsorption hydrogen bond network. In contrast, of small gold clusters to the cerium the excited states of curcumin in oxide surface has been proposed to 66γCD2su and 66γCD2ur show an facilitate this process. incomplete recovery, even at t > 2.5 ns. We propose that 66γCD2su We use DFT to calculate small Ce3On and 66γCD2ur restricts the hydrogen and AuCe3On (n=1,..,6) clusters as bond network between curcumin model surface analogues to study and water molecules, leading to the effects of gold adsorption on ineffective solvent-mediated ESIHT. the cerium oxide surface. Our Therefore, deactivation of the excited calculations of the Ce3On cluster state curcumin relies on other slow show a decrease in the oxygen pathways including vibrational binding energy coupled with an relaxation, resulting in observed a increase in ionisation energy as the long decay time constant. cluster species become more highly oxidised. Furthermore, the Ce3O5 and Ce3O6 clusters are calculated to photo-dissociate in preference of photo-ionisation; this is consistent Poster 29 with our photo-ionisation produced mass spectra in which we are unable Robert A Hardy, Aidan M Karayilan, Gregory F Metha to detect these species. Similar The University of Adelaide trends for ionisation and oxygen binding energy are observed for the Density Functional Theory and AuCe3On cluster series, albeit with a ca. 2eV weakening in the oxygen Photo-Ionisation Studies of binding energy for the AuCe3O6 Gold-Cerium Oxide Clusters cluster compared to Ce3O6. We propose that gold facilitates the initial Abstract abstraction of oxygen atoms from the The potential for transition metal ceria surface by adsorbed reactants clusters deposited on metal oxide but does not increase the amount of surfaces to catalyse industrially oxygen available for reaction. and environmentally relevant heterogeneous processes such as the water gas shift reaction and CO oxidation/NOx reduction has sparked intense research within the nanocatalysis industry. Particular interest has been directed toward gold clusters chemisorbed to cerium oxide surfaces which have been shown to catalyse low temperature oxidation reactions. The catalytic propensity of these systems has been attributed to the low oxidation 110 www.physchem2013.com.au Poster 30 which are diagnostic of the different TCNQF4 oxidation states. Some Dr Naomi Haworth1,2, Dr Chris Thompson1, vibrational frequencies, particularly Dr Jinzhen Lu1, Nguyen Vo1, the nitrile stretching modes, are A/Prof Lisa Martin1, Thanh Le1, Alan Bond1 extremely sensitive to the crystalline environment of the molecule. We 1. Monash University, have also explored the effects of 2. Deakin University nearby charged species within crystal lattices on the molecular Identification of TCNQF4 and electronic properties of TCNQF4 Oxidation States via species. Experimental and Theoretical One particularly interesting Vibrational Spectra characteristic of experimental Abstract TCNQF4- and TCNQF42- infrared spectra is that bands are often 2, 3, 5,6 -tet ra fl uo ro -7,7, 8 , 8 - observed corresponding to tetracyanoquinodimethane, TCNQF4, symmetric modes which would is an intriguing molecule which has normally be expected to be infrared extensive π-bonding throughout its silent. We probe the nature of structure. Upon reduction, either these transitions and explain the mono- or dianionic molecular ions spectroscopic phenomena which can be formed, both of which show allow them to absorb infrared light. delocalisation of the π electrons. These systems have therefore been of great interest for the synthesis of coordination polymers with useful magnetic and electronic properties. Poster 31 However, characterisation of the TCNQF4 oxidation state(s) present Alireza Heidari, Pravindya Haputhanthri, in these materials has often been Dr Ekaterina Izgorodina, A/Prof Bayden Wood challenging. Infrared and Raman Monash University spectroscopy provide valuable tools for this purpose; however their usefulness has been hampered by Analysis of conformations confusion over peak assignments and and vibrational frequencies lack of understanding of the impact of AMP, ADP, and ATP: A of reduction on the vibrational combined computational and spectra. experimental study

We have used density functional Abstract theory (B3LYP/6-31(2df,p)) to probe the changes in molecular and In the previous ground breaking electronic structure as well as work by our group it was reported variations in (and mixing of) the that the conformation of DNA is TCNQF4 vibrational modes as the strongly dependent on hydration molecule is reduced. This has allowed in cells and isolated nuclei.1 While us to clarify the peak assignments this phenomena is well known for and identify spectral characteristics isolated DNA it had not be previously 111 www.physchem2013.com.au reported in cells and isolated nuclei. perform geometry optimisations with The A-DNA form is prevalent when subsequent frequency calculations. the humidity drops below 75%, Both MP2 and DFT-based methods while above this level the B-DNA were combined with a series of basis form dominates. The main spectral sets ranging from traditional Pople’s differences observed going form basis sets to correlation-consistent the hydrated B-DNA form to the Dunning’s basis sets. The computer- dehydrated A-DNA form include: (1) generated spectra are compared a shift in the υassym(PO2-) from ~1225 with experimental spectra recorded cm-1 to ~1240 cm-1 band, (2) a using Attenuated Total Reflectance reduction in intensity of the υsym(PO2-), Fourier transform infrared (ATR-FTIR) and (3) a shift in the base stacking spectroscopy. In this presentation a mode at ~1715 cm-1 to ~1710 cm-1. detailed comparison between the In order to gain an understanding calculated and experimental results into the origin of these spectral will be presented. changes we have applied a range of computational chemistry methods Key Words to model single nucleotides such as AMP, ADP, ATP, Nucleotides, MP2, DFT, AMP, ADP, and ATP to predict their Basis sets, Gas phase, Explicit solvent, vibrational frequencies and infrared Implicit solvent, Conformations, ATR-FTIR intensities with the aim to establish spectroscopy a computational methodology References for studying more complex oligonucleotides and ultimately DNA (1) Whelan, D. R.; Bambery, K. R.; Heraud, itself. The goal of the study was two- P.; Tobin, M. J.; Diem, M.; McNaughton, D.; Wood, B. R. Nucleic Acids Res 2011, 39, fold: (1) investigate the influence of 5439-5448. explicit and implicit solvents on the stretching and bending vibrations Acknowledgments associated with the phosphodiester The authors would like to acknowledge bonds and the nucleic bases and sincerely thank the Monash including AMP, ADP, and ATP and (2) e-Research Centre, the National compare the performance of various Facility of the National Computational quantum chemical methods for the Infrastructure, and Multi-modal Australian prediction of vibrational frequencies ScienceS Imaging and Visualisation and intensities of simple nucleotides. Environment for a generous allocation of The implicit solvent was treated computational resources. though a Conductor-like Polarisable Continuum Model (CPCM) using water as solvent, whereas for the explicit solvent water molecules were placed around the nucleotide. A wide range of density functional theory (DFT) methods such as B3LYP, M06L, M06, M062X, B97D, PBE, PBE1, TPSS, TPSSh, LC-BLYP, LC-wPBE, B2PLYP, and mPW2PLYP were selected. Among ab initio methods a second order perturbation theory method, MP2, was the only feasible method to 112 www.physchem2013.com.au Poster 32 membrane, in three dimensions with super-resolution and in a time- Dr Clare Henderson1,3, Edward Nagul2,3, resolved manner. A/Prof Trevor Smith1,3, Prof Spas Kolev2,3 We have imaged poly(vinyl chloride)- 1. ARC Centre of Excellence for Coherent based PIMs with Aliquat 336 as carrier X-ray Science, 2. Centre for Aquatic after extracting fluorescein from Pollution Identification and Management, aqueous solution using confocal and 3. The University of Melbourne structured illumination microscopy.2 We observed that there exist Imaging Chemical preferential extraction zones within Extraction by Polymer the membrane which increase in Inclusion Membranes Using size dependent on immersion time in Fluorescence Microscopy the fluorescein solution. Importantly, correlation of these zones with Abstract surface morphology was not found. Polymer inclusion membranes We have applied time- (PIMs) extract chemical species resolved confocal fluorescence from solution1 and show promise microspectroscopy3 to probe the for trace environmental analysis changes in the properties of PIMs and removal of heavy metals and with ageing. Clear differences in the toxic anions in waste water clean time-resolved emission characteristics up. The mechanistic details of are observed between PIMs that how they work, however, are still are infused with fluorescent solution unclear. Some promising PIM types compared with membranes that must be conditioned before use have been used to extract the and the membranes are initially fluorophore. Fluorescence decay flexible but become brittle, and less time distributions evolve as the efficient extracting devices with PIM ages associated with the film age, limiting their potential on the stiffening with age. industrial scale. Why PIMs exhibit this time dependency is also not well Extraction of a molecular rotor understood. fluorescent probe4 was used to measure the microviscosity of the Few techniques are available that membrane to correlate changes can probe these properties with in the PIM efficacy with stiffness the required spatial resolution and, and brittleness of the membrane historically, methods must infer as it ages. Fluorescence anisotropy PIM function from probing surface measurements have also been used morphology only. By uptaking a to probe the films’ internal viscosity. fluorescent dye, however, we can image the PIMs with a range of fluorescence microscopy methods traditionally associated with the biological sciences. This allows us to see the extraction and transport processes both laterally and as a function of depth within the

113 www.physchem2013.com.au By applying a range of fluorescence microscopy methods, we have been able to see the extraction of chemical species within the PIMs. This work demonstrates a novel probing method for understanding PIM function and will no doubt inform the design of more stable and efficient PIMs.

References [1] M.I.G.S Almeida, R.W. Cattrall and S.D. Kolev, “Recent trends in extraction and transport of metal ions using polymer inclusion membranes (PIMs)”, J. Membrane Sci., 415-416, 9-23 (2012)

[2] T.A. Smith, L.M. Hirvonen, C.N. Lincoln and X. Hao, “Deep-UV confocal fluorescence imaging and super- resolution optical microscopy of biological samples”, J. Innov. Opt. Health Sci. 5(4) 1250025/1-9 (2012)

[3] X. Hao, L.M. Hirvonen and T.A. Smith, “Nanomorphology of polythiophene- fullerene bulk-heterojunction films investigated by structured illumination optical imaging and time-resolved confocal microscopy”, Meth. Appl. Fluor. 1, 015004/1-8 (2013)

[4] J.A. Levitt, P.-H. Chung, M.K. Kuimova, G. Yahioglu, Y. Wang, J. Qu,and K. Suhling, “Fluorescence Anisotropy of Molecular Rotors”, ChemPhysChem, 12, 662 – 672 (2011) M.K. Kuimova, G. Yahioglu, J.A. Levitt and K. Suhling, “Molecular rotor measures viscosity of live cells via fluorescence lifetime imaging”, J.A.C.S., 130, 6672-6673 (2008)

114 www.physchem2013.com.au Poster 33 polarised emission and a potential material for data storage.4 Heather Higginbotham1, Dr Tich Lam Nguyen2, Dr Alison Funston1, We have visualised the optical Prof Paul Mulvaney2, Dr Toby Bell1 properties of quantum nanocrystal 1. Monash University, materials using defocused widefield 2. The University of Melbourne microscopy. Much like conventional widefield techniques defocused Investigation of the optical and widefield applies a focused and collimated laser onto the back focal emission properties of CdSe plane of an objective. However nanocrystals using defocused by “defined image defocusing” or widefield microscopy the introduction of an aberration in the path of the objective further Abstract information about the angular One of the most researched distribution of fluorescence intensity fluorescent materials of the may be obtained.5 We report the last decade is semiconductor synthesis, optical characterisation nanoparticles or quantum dots. and defocused widefield imaging Quantum dots are clusters of of CdSe quantum nanocrystals of crystalline semiconducting varying shapes. All nanocrystals materials, commonly synthesised were characterised using UV-visible from Zn, Cd and Pb metals and Se spectroscopy, TEM, and widefield chalcogenides; the most common microscopy. We show that unlike of these synthesised from cadmium the CdSe spheres that have been and selenium. With sizes ranging from previously show to contain no a few hundred to a few thousand discreet emission dipole, more atoms CdSe quantum dots can be complex shapes such as CdSe highly fluorescent, are extremely rods contain a single and discreet photostable, have a large absorption emission dipole. Figure 1a shows cross section and a high resistance defocused widefield images of CdSe to photobleaching.1 Unlike bulk spheres with an emission pattern semiconductor materials quantum characteristic of a multi-dipole dots have a tunable bandgap and emitter already characterised in therefore fluorescence emission is the literature. Figure 1b shows that directly related to the size of the the emission patterns of CdSe rods, quantum particle. however is easily characterised as a single dipole emitter. Shape control of semiconductor nanocrystals has now been achieved by modifying the method of synthesis creating nanoparticles in a range of shapes including spheres, rods, rice, and tetrapods.2,3 Shape alteration should affect optical properties, in particular, quantum rods may adopt a magnetic dipole along the long axis of the wurzite structured Figure1: a) emission pattern of CdSe nanocrystals leading to linearly spheres b) emission pattern of CdSe rods 115 www.physchem2013.com.au Poster 34 0.3 Å. A base-doped Grotthus mechanism allows greater ease of Dr Jennifer Hodgson, Ahmed Halima, motion of anions and lowering of the Dr Ekaterina Izgorodina, Prof Douglas barrier, with reactions requiring little MacFarlane translational and rotational motion. Monash University However, the more anions there are present the shorter the distance the Barriers for Proton Transport charge is transferred. In almost pure in Hydrogen-bound Systems acid the H-bonded chains are longer leading to longer proton transfer Including Protic Ionic Liquids distances. In this case, however, the Abstract motion of molecules is hindered by the H-bonding and unfavourable There is growing interest in the polarisation of the chain, leading to a application of protic ionic liquids higher barrier for proton conductivity. in fuel cells and water splitting. In Solvent reorganisation is required both cases an understanding of in order to extend the distance the kinetic and thermodynamics of charge transfer. This work will of proton transfer is critical. It has attempt to further understand the been known for some time that neat effect of differing amounts of base- acids containing intermolecular doping on the intermolecular proton hydrogen bonding show high intrinsic conductivity of neat acids and protic intermolecular proton conductivity, ionic liquids. with proton transport occurring through a Grotthuss-type mechanism References similar to the transport of excess (1) Berkelbach, T. C.; Lee, H.-S.; Tuckerman, charge defects in water.1 Pervious M. E. Phys. Rev. Lett. 2009, 103, 138305. studies have focused on proton conduction in neat phosphoric (2) Vilciauskas, L.; Tuckerman, M. E.; Bester, acid in order to further understand G.; Paddison, S. J.; Kreuer, K.-D. Nature mechanism for phosphate-based Chem. 2012, 4, 461. systems such as phosphonated polymers and biological systems such as adenosine triphosphate (ATP).2 However, the same processes occurring in acetic, sulphuric and triflic acid systems have received little attention.

In this work we use computational chemistry to investigate the barriers and mechanisms of proton transfer reactions in these acids. Energy profiles show that the barriers for these reactions are low, as expected. While the charges can be transported by this mechanism over large distances, the movement of individual protons is less than 116 www.physchem2013.com.au Poster 35 Good agreement between experiment and theory verifies the Aidan Karayilan, A/Prof.Gregory Metha structure of the clusters formed and The University of Adelaide allows further analysis such as the mechanism of charge transfer upon Experimental and reaction as well as the preferred binding sites of the transition metal Computational Studies on component. Bimetallic Clusters of Platinum and Cerium

Abstract Poster 36 The interactions between reactant molecules and catalytic systems Dr Tak Kee1, Yin Song2, composed of nanoparticles or Dr Yoichi Kobayashi2, Dr Ryan Pensack2, clusters deposited on metal oxide Prof Gregory Scholes2 surfaces are difficult to study due to their varying composition (cluster 1. The University of Adelaide, aggregation, nanoparticle size 2. University of Toronto distribution, defect sites). As such, it is proposed that the interaction Mapping Charge Generation be studied by focussing only on the in an Organic Semiconductor isolated site at which the catalysis using Two-Dimensional Photon occurs. This can be done by forming and studying gas-phase clusters, Echo Spectroscopy both isolated and in the presence Abstract of reactant gas molecules, such as carbon monoxide. Two-dimensional (2D) photon echo spectroscopy is a nonlinear optical Clusters of platinum and cerium spectroscopic technique that oxide are generated via a dual relies on the third-order nonlinear laser ablation source coupled susceptibility of materials. This with tuneable dye laser ionisation technique, which is the optical and linear time-of-flight mass analogue of 2D NMR and 2DIR, offers spectrometry. Cluster ionisation the opportunity to characterize the energies are determined using coupling between vibronic transitions photo-ionisation efficiency (PIE) within a system. In the spectrometer spectroscopy, and compared with used for the present study, the theoretical ionisation energies output of a 12-fs laser with a central from density functional theory wavelength and band width of 580 calculations. Additionally, Franck- nm and ~100 nm, respectively, is Condon (FC) calculations are split into four equal replicas using performed on the computationally a diffractive optic in the boxcar derived structures to yield simulated geometry. The first three outputs are Zero Electron Kinetic Energy (ZEKE) independent delayed in time using spectra, which are then used to pairs of glass wedges. The generated construct simulated PIE spectra, third order signal is then interfered against which the experimental with the fourth output (local spectra are compared. oscillator) on a CCD spectrometer 117 www.physchem2013.com.au to yield spectral interferograms. Poster 37 Fourier analyses of the wavelength dependent interferograms results Thomas Keevers1, Andrew Danos2, in 2D contour plots that contain Dr Karl Weber3, Dr Scott Watkins3, information on coupling of vibronic Dr Dane McCamey1 transitions. 1. University of Sydney, In this study, 2D photon echo 2. University of Sydney, 3. CSIRO Materials Science and spectroscopy is used to investigate Engineering nanosized aggregates of the conjugated polymer poly(3- hexylthiophene) (P3HT) doped with Probing Spin-Dependent PCBM, which is a fullerene derivative. Transport and Recombination It is well established that P3HT has in Organic Light-Emitting distinct vibronic transitions, e.g., Diodes through Magnetic the 0-0, and 0-1 transitions, with wavelengths of 600 nm and 560 Resonance nm, respectively. Photoexcitation of Abstract the nanosized aggregates using a wavelength within these transitions The significant disorder and generates excitons (excited state) in weak Coulombic screening of the P3HT domains. Migration of the organic semiconductors leads excitons to domains of PCBM, which to sophisticated spin-dependent function as electron acceptors, transport and recombination [1]. enables charge transfer reactions, These pathways have typically been whereby electrons are transferred investigated through magnetic to the PCBM domains and the resonance at strong magnetic fields, resulting positive charges (hole where the energetics is dominated polarons) reside in the P3HT domains. by the Zeeman splitting. This scenario The presence of hole polarons is is somewhat unrealistic in that often characterized by an induced technological applications typically absorption band around 650 nm. The take place at smaller fields, where 2D photon echo results show clear zero-field splitting is expected to cross-peaks between the polaron play a substantial role. A canonical absorption band and both the 0-0 example of a low-field effect is and 0-1 transitions. Further analyses Organic Magnetoresistance, the of the cross-peaks show that the large changes in resistivity (~10%) vibrational coherence consisting of seen at small magnetic fields (<50 mT) the C=C bonds of P3HT is involved in [2]. the charge transfer reaction. These results offer further insight into the The electrical and optical pathways photovoltaic effect of P3HT. of organic semiconductors can be described through the polaron pair model, in which weakly coupled electron-hole pairs are able to dissociate into free charge carriers, or form strongly exchange-dominated excitons [1]. These pairs display spin-dependent behaviour through 118 www.physchem2013.com.au preferred recombination through the Poster 38 singlet channel, and slower carrier transport in the triplet configuration Julie Kho, A/Prof Peter Boyd , [3]. Despite the importance of spin Dr Ali Hosseini , A/Prof Cather Simpson in organic devices, many basic The University of Auckland questions are without consensus, such as the dominant spin relaxation Photochemical Studies of Self- mechanism. Assembled Porphyrin-fullerene We have custom-built a cryostat Complexes through Transient system which allows us to perform Absorption Spectroscopy pulsed electrically and optically detected magnetic resonance at Abstract low-field strengths, and at a variety Porphyrin-fullerene assemblies were of temperatures. This will provide discovered over a decade ago as insight into the spin dynamics which potential artificial photosynthetic govern optoelectronic efficiencies, mimics due to their photoinduced, and identify the role of thermally- multistep electron transfer activated processes. We will perform behaviour1. A new class of calix[4] field-swept pulsed Electrically arene-linked bisporphyrin (“jaws” Detected Magnetic Resonance porphyrin) has been constructed (pEDMR), as described by Baker that bind fullerene with high affinity2. et al [4], on iridium-doped OLEDs Understanding of the photochemistry with strong spin-orbit coupling. To of these self-assembled complexes, our knowledge, this situation has in particular the charge-separated not been investigated theoretically state lifetime is the focus of this or experimentally, and will identify study. For this purpose, state-of-the- the effects of spin-orbit coupling art, near-IR transient absorption on the dynamics of spin resonance spectroscopy (TrA) has been utilized in organics. Our devices contain to measure the excited state lifetime a variety of blend ratios, and this of fulleride C60-. will provide secondary information relating to the structural and spin In this report, we show results from coupling effects caused by iridium- two different sets of bisporphyrin- doping. fullerene triad systems. The first set is a completely self-assembled system in [1] J. M. Lupton, D.R. McCamey, C. which a ferrocene secondary donor Boehme, ChemPhysChem, 11, 14, 3040- is coordinated to the Zn-porphyrin 3058 (2010) primary donor. In the second set, self-assembled porphyrin-fullerene [2] Y Sheng et al, Phys Rev B, 74, 045213 (2006) systems are constructed with a variety of distances between the [3] A. Schnegg et al, Phys. Chem. Chem. covalently bounded secondary Phys, 14, 14418-14438 (2012) donor and the primary donor.

[4] W.J. Baker, et al, Nat Comm, 3, 898 When photoexcited, the porphyrin (2012) donates an electron to the fullerene acceptor. This charge-separation step to form the porphyrin cation and 119 www.physchem2013.com.au fullerene anion occurs within the tens Initial TrA studies of novel solid-state of picoseconds. In the triad system, porphyrin-fullerene constructs have a second electron transfer step from been performed as well. These ferrocene to the porphyrin separates samples have been prepared using the charges further in distance. This self-assembled, co-crystallized additional electron step should slow structures of various porphyrins with the charge recombination process, fullerene grounded with KBr into <0.5 and give rise to a longer charge- mm thick discs. Crystal structures separated state lifetime. were characterized using X-ray crystallography, and show ordered First, we investigated the porphyrin and fullerene packing. bisporphyrin-fullerene dyad (Figure The TrA results showed the effects of 1) in two different solvents (toluene, this packing on the lifetimes of the cyclohexane) which showed that a charge-separated state to explore higher binding constant of C60 to the effects of crystal packing on the porphyrin in cyclohexane leading to electron transfer process. faster charge combination (lifetimes = 560ps and 430ps, toluene and [1] (a) Kuciauskas, D.; Lin, S.; Seely, G. cyclohexane, respectively). We also R.; Moore, A. L.; Moore, T. A.; Gust, D.; observed a longer lifetime (2.5 ns) Drovetskaya, T.; Reed, C. A.; Boyd, P. D. W., Energy and Photoinduced Electron when a tert-butyl pyridine group Transfer in Porphyrin−Fullerene Dyads. is coordinated to the bisporphyrin The Journal of Physical Chemistry 1996, complex. Unexpectedly, the 100 (39), 15926-15932; (b) Imahori, H., ferrocene-pyridine coordinated Porphyrin-fullerene linked systems as triad complex showed no evidence artificial photosynthetic mimics. Organic of secondary electron transfer, & Biomolecular Chemistry 2004, 2 (10), suggesting that its extended lifetime 1425-1433. of 1.5 ns is a coordination effect. A [2] Hosseini, A.; Taylor, S.; Accorsi, G.; relationship between electronic Armaroli, N.; Reed, C. A.; Boyd, P. D. W., coupling and lifetimes of the Calix[4]arene-Linked Bisporphyrin Hosts charge-separated state has been for Fullerenes: Binding Strength, Solvation demonstrated. For the second set of Effects, and Porphyrin−Fullerene Charge bisporphyrin fullerene, we observed Transfer Bands. J. Am. Chem. Soc. 2006, an increase in charge-separated 128 (49), 15903-15913. lifetime (from 1 ns to 3 ns) with increasing distance of the secondary Figure 1: (Below) An example of the calix[4]arene-linked bisporpyrin-fullerene donor to primary donor. constructs (left). A nIR transient absorption spectrum showing decay of C60- signal.

120 www.physchem2013.com.au Poster 39 Poster 40

Michael Morris1,2, Dr Bun Chan1,2, Prof Leo Miranda Shaw, Brian Yates Radom1,2 University of Tasmania

1. The University of Sydney, 2. ARC Centre of Excellence for Coherent DFT Studies of N2O Reactivity X-Ray Science (CXS), with Vanadium and N-Heterocyclic Carbenes Excellence for Free Radical Chemistry and Biotechnology Abstract How do Bond Dissociation Enthalpies N-Heterocyclic carbenes have Depend on Protonation State? been shown to form stable adducts with kinetically inert nitrous oxide. Abstract Following exposure to vanadium(III) The effect of protonation and complexes, both the NO and NN deprotonation on the strength bonds are sequentially broken, of chemical bonds is a topic in a mechanistically different of particular interest, not least reaction to most known metal-N2O because of the prevalence of interactions[1]. The current DFT study proton-transfer reactions. In this has shown that the reaction proceeds connection, we have used high- by coordination of the NHC-N2O level ab initio calculations to look at adduct to the d2 metal centre of VR3 how bond dissociation enthalpies complexes (R = methyl, mesityl), to (BDEs) change as a result of both form an initial η1-O triplet complex, adjacent and remote protonation from which several reaction paths are or deprotonation, including partial available, on both the singlet and protonation and deprotonation. triplet surfaces. Trends in the related gas-phase acidities are also explored, as is the The experimental reaction was shown effect of placing various interposing to proceed by intersystem crossing connector groups on the BDEs. to yield an η2-O,N singlet complex, The protonation states considered which in turn isomerizes to a highly provide a first approximation to the reactive η3 complex in which all three effect of an aqueous solvent on BDEs atoms of the nitrous oxide molecule for a range of pH values. are coordinated to the vanadium. NO bond cleavage and simultaneous ligand migration then occurs with a 32 kJ mol-1 barrier, producing the lower energy vanadium-oxo complex containing a hydrazone-like ligand. The second NN bond cleavage then occurs with a much higher barrier of approximately 130 kJ mol-1, though Figure 1. The methanol-water complex, a the calculated energies for both model for partial protonation. reactions are consistent with the experimental reaction conditions. [1] Morris, M.; Chan, B.; Radom, L. J. Phys. The presence of the carbene Chem. A 2012, 116, 12381¬–12387. changes the expected reactivity 121 www.physchem2013.com.au of the nitrous oxide (which typically and the anticipated uptake of FTIR releases molecular nitrogen following spectroscopy in clinical settings also oxygen abstraction) by directly remains elusive. This is, at least in increasing electron density on the part, due to the discovery of several terminal nitrogen, which in turn artefacts in the infrared spectrum of greatly increases the Lewis basicity biological samples. Several of these of the internal nitrogen, allowing it are now known to be due to physical to strongly coordinate to the metal interactions between the sample and undergo further insertion and and the infrared light and can be addition reactions. The relatively removed using algorithms. Our low energies associated with these research has focussed on deducing reactions show that the nitrous oxide the cause of the so-called “Dark has potential to be exploited as a DNA” effect and on demonstrating useful source of both oxygen and the sensitivity of FTIR spectroscopy to nitrogen for organic synthesis. nucleic acid absorptions. The “Dark DNA” effect was based on infrared [1] Tskhovrebov, A. G.; Solari, E.; Wodrich, spectra of cells that appeared to M. D.; Scopelliti, R.; Severin, K. J. Am. be missing DNA-specific absorptions Chem. Soc. 2012, 134, 1471–1473. (1). Because of this, the DNA was hypothesized to be opaque to infrared light due to its high level of compaction. As this was a non- Poster 41 Beer-Lambert interaction and not easily quantified or corrected for, it Donna Whelan1, Dr Keith Bambery2, was cited often as a confounding Dr Ljiljana Puskar2, Prof Don McNaughton1, variable in research attempting to Ass/Prof Bayden Wood1 detect cancer and precancer based on DNA absorptions. By working with 1. Monash University, fully hydrated cells we were able to 2. Australian Synchrotron detect a reversible conformational change of the native B-DNA to Fourier Transform Infrared A-DNA during dehydration that Spectroscopic Detection of also coincided with a decrease DNA in Cells in absorption intensity. More importantly we found this transition Abstract to be reversible both in eukaryotes Fourier transform infrared (FTIR) (2) and, more recently, in functional spectroscopy offers a non-invasive prokaryotes. method for holistically measuring and ‘fingerprinting’ the entire biochemical Following this and in a further composition of a sample. Because effort to explain the “Dark DNA” of this, it has long been highlighted effect, we attempted to quantify as a potential method for disease DNA spectroscopically in avian detection, diagnosis, monitoring and erythrocytes. To do this we understanding as well as in a broader constructed regression models based sense as a fundamental biochemical on standards on known protein/DNA technique. However actualization dry weight ratios. The spectra of avian of this potential has not occurred erythrocytes and extracted nucleic were then fitted to the regression 122 www.physchem2013.com.au models to yield accurate estimates of References DNA content (average experimental: (1) B. Mohlenhoff, M. Romeo, M. Diem, B. 44.2±6.6% in nuclei, 12.8±4.3% in R. Wood, Biophys. J. 88, 5, (2005), 3635. erythrocytes, actual: 44.3% in nuclei, 12.5% in erythrocytes) (3)). This result (2) D. R. Whelan, K. R. Bambery, P. Heraud, demonstrated the Beer-Lambert M. J. Tobin, M. Diem, D. McNaughton, B.R. Wood, Nuc. Acid. Res. 39, 13 (2011), 5439. nature of the absorption of infrared light by cellular DNA and further work (3) D. R. Whelan, K. R. Bambery, L. determined that absorption changes Puskar, D. McNaughton, B. R. Wood, were due to a change in the molar J. Biophotonics, (2012) doi: 10.1002/ extinction coefficient. jbio.201200112.

Most recently, spectra of >500 (4) D. R. Whelan, K. R. Bambery, L. Puskar, live hydrated cells of known age D. McNaughton, B. R. Wood, Analyst, 138, (2013), 3891. post-mitosis (throughout the G1, S and G2 phases) were acquired at the Australian Synchrotron. Principal Component Analysis of the fingerprint and CH2/CH3 regions of the spectrum allowed successful separation of cells only two hours apart and within the same phase based on changes in DNA, protein and lipid concentration as well as changes to secondary structure and lipid ordering (4). This level of sensitivity achieved non-invasively with live cells is unprecedented and demonstrates the ability of FTIR spectroscopy to detect very subtle biochemical changes in cells. It is anticipated that the ability to consider DNA absorptions in FTIR spectra both quantitatively and with regards to conformation will lead to detection of changes in cell proliferation rate and aneuploidy allowing for detection of cancerous cells.

123 www.physchem2013.com.au Poster Session 2 vectors are independent. Angular momentum is explicitly included in the second PST calculation; the HCO angular momentum is set to that arising from the first PST step. Poster 42 There are no adjustable parameters in the model; the parameters are all Duncan Andrews, Nicholas Hobday, provided by spectroscopic data or Mitchell Quinn, Dr Klaas Nauta, ab initio calculation. The double PST– A/Prof Meredith Jordan, Prof Scott Kable impulsive model provides a good fit The University of Sydney to experimental speed and energy distributions for H2CO dissociation on An Impulsive Phase Space S0. Speed and energy distributions Theory for Triple Fragmentation have been modelled for H atom and CO fragments for available energies Abstract spanning over 7000 cm-1 and 1000 We describe a simple model for cm-1 respectively. H-atom yields simulating product state distributions (%) arising from reaction on the S0 in sequential triple fragmentation (3F) and T1 surfaces are also obtained, reactions, that is, where a molecule at energies below and above the breaks into two “hot” fragments and 3F threshold, from the difference one of these subsequently dissociates between experimental and simulated on a time scale longer than its H atom speed distributions. We show molecular rotational period. The that the triplet mechanism slowly model was initially developed to diminishes in importance for energies simulate H atom and CO fragment in excess of the triplet barrier and speed, energy and angular that triple fragmentation becomes momentum distributions for H2CO increasingly important as the 3F dissociation on S0 above the threshold energy is exceeded. The 3F threshold. This reaction is modelled 3F model is also applied to CH3CHO, as a two-step process. Initially, CH3OCHO and CH3OCH3 and used barrierless C-H bond fission on S0 to discriminate products arising from forms H + HCO. Those HCO radicals 3F and products arising from with sufficient internal energy to “roaming” reactions. overcome the small exit channel barrier on the HCO surface undergo Figure 1. For 6943 cm-1 of available secondary fragmentation to form H energy, an experimental H-atom speed distribution and calculations for a) no + CO. Our model treats the first step secondary fragmentation; b) secondary using phase space theory (PST) and fragmentation with no barrier in the HCO the second using a combined PST- exit channel; c) including the effect of impulsive model, with a tunneling a 700 cm-1 exit channel barrier; and d) correction. The final velocity of allowing tunneling through the barrier. products from the second step is obtained as the vector sum of the HCO parent velocity from the first fragmentation and the velocity imparted to the product fragment during the second fragmentation, assuming that the directions of these 124 www.physchem2013.com.au semiconductors and insulating crystals. Using energies from molecular ab initio calculations at an arbitrary level of theory, the method can model a wide range of properties from structure and lattice dynamics to defect energies. We have applied this fragmentation method to surfaces cleaved from crystals and their interactions with gas phase molecules. Furthermore, the method has been constructed to allow modified Shepard interpolation of the potential energy surface (PES) of each molecular fragment, thus defining the PES of the gas–surface interaction. The dynamics of the gas–surface system can be used to direct sampling of the constituent molecular PESs for building the interpolations. Thus the dynamics of the gas–surface system can be converged with respect to the PES sampling with automatic molecular configuration biasing relevant to the fragmented gas–surface system. While the fragmentation is performed under crystal symmetry, there is no requirement to maintain space group Poster 43 or translational symmetry in the subsequent study of the dynamics. Dr Terry Frankcombe Australian National University The approach is demonstrated by applying it to hydrogen radicals impacting onto a hydrogen- Calculating the energetics and terminated silicon (111) surface. Cross dynamics of the interaction of sections have been calculated for molecules with semiconductor a number of processes including surfaces using fragmentation non-reactive scattering, hydrogen and ab initio calculations: abstraction and a range of sticking processes. hydrogen atoms and hydrogen-terminated silicon (111)

Abstract Collins et al. have developed a fragmentation-based methodology for studying large band gap

125 www.physchem2013.com.au Poster 44 [6] J.A. Sebree, V.V. Kislov, A.M. Mebel, T.S. Zwier, J. Phys. Chem. A 114 (2010) 6255 Dr Olha Krechkivska, Dr Klaas Nauta, Prof Scott Kable, Prof Timothy Schmidt The University of Sydney

A new way to add hydrogen to aromatics: REMPI studies of benzene+H, toluene+H, naphthalene+H

Abstract A new method for generating hydrogenated aromatics has been discovered. Our method has been Figure 1. REMPI spectra of hydrogenated tested on a few different molecules, and deuterated aromatics such as benzene+H, naphthalene+H that have a known optical spectrum in the gas phase,1-6 as well as a new system, toluene+H that has not been Poster 45 studied prior to this work. Argon gas containing water vapour was passed Cara Kreck, Prof Ricardo Mancera through samples of benzene, toluene Curtin University or naphthalene and hydrogenated species were produced in an Molecular dynamics electrical discharge followed by supersonic expansion. The role of simulations of the glass water being the source of hydrogen transition of water using was proven using D2O vapour in the different intermolecular carrier gas, producing deuterated potentials species, while using fully or partially deuterated aromatics with H2O led Abstract to the creation of hydrogenated Effective vitrification of water is radicals only. essential for the successful long- [1] M.C. Sauer Jr., B. Ward, J. Phys Chem. term storage of biological tissues 71 (1967) 3971 through cryopreservation. This method applies ultrafast cooling [2] T. Shida, I. Hanazaki, Bull. Chem. Soc. rates to induce the formation of the Jpn 43 (1970) 646 glassy state of water at extremely low temperatures with the help [3] S.J. Sheng, J. Phys. Chem. 82 (1978) 442 of cryosolvents, thus avoiding the damaging formation and growth [4] M. Nakajima, T.W. Schmidt, Y. Sumiyoshi, Y. Endo, Chem. Phys. Lett 449 of ice crystals and indeed arresting (2007) 57 all physical and biochemical processes. Molecular dynamics [5] T. Nakayama, S.J. Sheng, Mol. Cryst. simulations allow detailed study Liq. Cryst. 69, (1981) 199 of the experimentally inaccessible

126 www.physchem2013.com.au liquid state of supercooled water the maximum in the derivative of below its homogeneous nucleation the density. In the NVT ensemble, temperature, and have enabled the these points are instead related to characterisation of the glass transition the maximum in the internal pressure of water promoted by cryosolvents and the minimum of its derivative, (1, 2). respectively. A detailed analysis of the hydrogen bonding properties at Simple, non-polarisable the glass transition provide further intermolecular potential models insight into the differences between are commonly used in classical each water potential investigated. MD simulations of water and aqueous systems due to their low References computational cost and their 1) Kreck, Mandumpal & Mancera, Chem ability to reproduce a wide range Phys Lett, 2011, 501, 273-277. of thermodynamic, structural and dynamical properties. As the quality 2) Mandumpal, Kreck &Mancera, Phys of these predictions vary between Chem Chem Phys, 2011, 13, 3839-3842. the potentials, the predicted glass transition of water is likely to be influenced by the choice of potential. We have thus conducted an Poster 46 extensive comparative investigation of various three, four, five and six Kelvin Lee, Stephen Kolmann, Mitchell point water models in both the NPT Quinn, Dr Klaas Nauta, Prof Scott Kable, and NVT ensembles. A/Prof Meredith Jordan The University of Sydney Predictions of the glass transition temperature (Tg) for each water Quasi-Classical Trajectories on potential reveal that, in the NPT a Zero-Point Energy Corrected ensemble, the number of interaction Potential Energy Surface points in the model appears to be related to the position and height Abstract of the peak in the associated heat capacity change. The glass Classical molecular dynamics do transitions in the NVT ensemble not include quantum mechanical occur in the same order as in the NPT expectation values such as Zero- ensemble, but the heat capacity Point Energy (ZPE)1. Despite this peaks have different heights shortcoming, a classical framework and slopes, with the most striking is still favourable for computational changes occurring in the TIP4P family ease. Previous attempts to “fill” the of potentials. The change in Tg from ZPE leak have required complex NVT to NPT appears to be correlated holonomic constraints2-4 that have to the change in the magnitude and been showed to produce unphysical position of the maximum in the heat dynamics5,6. More recently, thse capacity change. The Tg from NPT problem has been circumvented by simulations is also strongly correlated discarding trajectories which violate with the temperature of minimum ZPE conservation, at the loss of density, whereas the maximum in the statistics and increased heat capacity plot corresponds to computational cost. One would 127 www.physchem2013.com.au expect this approach however, to be References unsustainable for larger systems. (1) Eyring, H. J. Chem. Phys. 1935, 3, 107. Instead, our group has benchmarked a consistent method of including (2) Bowman, J. M.; Gazdy, B.; Sun, Q. J. ZPE without introducing artificiality Chem. Phys. 1989, 91, 2859. in the product state distributions. As (3) McCormack, D. A.; Lim, K. F. Physical a proof-of-concept, we reproduced Chemistry Chemical Physics 1999, 1, 1–12. “Roaming” reaction dynamics in the bimolecular abstraction reaction (4) Czako; Kaledin; Bowman Chemical H+HCO -> H2 + CO on a modified Physics Letters 2010, 500, 6–6. Shepard Interpolated surface. In this work, we have included a zeroth- (5) Sewell, T. D.; Thompson, D. L.; Gezelter, order ZPE correction to the CASSCF J. D.; Miller, W. H. Chemical Physics Letters potential energy surface, with 1992, 193, 512–517. observables in good agreement (6) Guo, Y.; Thompson, D. L.; Sewell, T. D. J. with previous theoretical7,8 and Chem. Phys. 1996, 104, 576. experimental9,10 work. We have since extended the work to exploring the (7) Zhang, X.; Zou, S.; Harding, L. B.; reaction CH3CO + H -> CH4 + CO, Bowman, J. M. J. Phys. Chem. A 2004, 108, comparing with roaming 8980–8986.

(8) Zhang, X.; Rheinecker, J. L.; Bowman, J. M. J. Chem. Phys. 2005, 122, 114313.

(9) Townsend, D.; Lahankar, S. A.; Lee, S. K.; Figure : Reproduced correlations from Chambreau, S. D.; Suits, A. G.; Zhang, X.; our quasi-classical trajectory simulations Rheinecker, J.; Harding, L. B.; Bowman, J. between vibrational states of H2 and M. Science 2004, 306, 1158–1161. rotational states of CO. Rotationally cold CO fragments are correlated with (10) Lahankar, S. A.; Chambreau, S. D.; highly vibrationally excited H2, as seen in Zhang, X.; Bowman, J. M.; Suits, A. G. J. velocity-mapped imaging experiments9 Chem. Phys. 2007, 126, 044314.

128 www.physchem2013.com.au Poster 47 efforts to computationally design more durable PMMA, in the present Richmond Lee, Michelle Coote work we use quantum chemical Australian National University calculations to study the reactivity of ozone towards PMMA, reporting New Insights into herein the mechanism for ozone initiated polymer degradation and 1,2,4-trioxolane Stability depolymerisation.8 Our quantum and the Crucial Role of chemical calculations reveal that Ozone in Promoting Polymer common defects found in PMMA Degradation Richmond Lee such as a vinyl terminated chain end reacts expediently with ozone to Abstract form a 1,2,4-trioxolane intermediate 4 Poly(methyl methacrylate) (PMMA) (Figure 1). Subsequent decomposition and its derivatives are the primary of trioxolane involves intersystem constituents of many outdoor crossing from singlet 4 to triplet, products, such as paints and through the minimum energy crossing building materials, and are often point (MECP, calculated ΔEMECP = highly exposed to pollutants, heat +41.9 kcal/mol) and in the process and ultraviolet radiation (UV). A generates an alkyoxy biradical fundamental understanding of their intermediate 5 which causes further chemical degradation mechanisms chain degradation in a series of provides a crucial first step toward kinetic and thermodynamically the design of more resistant polymers. favourable processes. Whilst the conventional mechanism of polymer autooxidation assumes that oxygen plays a key role in helping to propagate autooxidative damage,1 there is growing evidence that for polymers such as PMMA, the situation is more complicated2-5 and that oxygen itself may even help to retard degradation.6, 7 Interestingly, previous studies have also revealed that nitric oxide retards PMMA degradation, 7 which has prompted Figure 1. Pathway for proposed ozone us to cast the spotlight on ozone, initiated polymer degradation. Values since NO reduces O3 to O2. are SMD/G3(MP2)-RAD//B3LYP/6-31+G(d) Intuitively, in absence of NO, O3 may Gibbs free energy in solution (kcal/mol) participate in PMMA degradation relative to starting materials. and play a more critical role in environmental polymer degradation References Ozone chemistry is of crucial [1] J. L. Bolland and G. Gee, Trans. importance in atmospheric science, Faraday Soc., 1946, 42, 236. plant biology, organic syntheses, drugs, and materials. Cognizant of [2] G. Gryn’ova, J. L. Hodgson and M. L. its huge and diverse impact and Coote, Org. Biomol. Chem., 2011, 9, 480- 490. in an attempt to consolidate our

129 www.physchem2013.com.au [3] F. Bennet, G. Hart-Smith, T. Gruendling, exists as the major species in most T. P. Davis, P. J. Barker and C. Barner- polar organic solvents, however Kowollik, Macromol. the tautomerisation is poorly Chem. Phys., 2010, 211, 1083-1097. understood. In this study, nuclear [4] F. Bennet, T. M. Lovestead, P. J. Barker, magnetic resonance spectroscopy T. P. Davis, M. H. Stenzel and C. Barner- is used to monitor deuteration of Kowollik, Macromol. Rapid Commun., curcumin at the α-carbon position 2007, 28, 1593-1600. in several deuterated solvents. The Hα peak around 6 ppm decays as a [5] F. Bennet, P. J. Barker, T. P. Davis, A. function of time, which is indicative H. Soeriyadi and C. Barner-Kowollik, of proton exchange of curcumin with Macromol. Chem. Phys., 2010, 211, 2034- deuterated solvent. Furthermore, the 2052. rate of tautomerisation of curcumin, [6] J. D. Peterson, S. Vyazovkin and C. A. which is inferred from the rate of Wight, J. Phys. Chem. B, 1999, 103, 8087- deuteration, is deduced by fitting 8092. the data using rate equations from a kinetic model. Additionally, the rate [7] H. R. Azimi, M. Rezaei and F. Abbasi, of tautomerisation exhibits a strong Thermochimica Acta, 2009, 488, 43-48. temperature dependence and the activation energy of tautomerisation [8] R. Lee and M. L. Coote, Phys Chem Chem Phys, 2013, submitted. of curcumin is determined in several polar organic solvents.

Poster 48 Poster 49 Mandy Leung, Prof Stephen Lincoln, 1 1 DrTak Kee Kamron Ley , Dr George Yiapanis , 2 3 The University of Adelaide Dr Dave Winkler , Dr Shane Maclaughlin , Dr Evan Evans3, Prof Irene Yarovsky1

A Kinetic Study of Keto- 1. RMIT University, Enol Tautomerisation of the 2. CSIRO Materials Science and Engineering, Medicinal Agent Curcumin 3. BlueScope Steel Research Laboratories with NMR Spectroscopy

Abstract Flexible or Rigid? Investigating the Effect of Surface hardness Curcumin, the major yellow pigment in turmeric, has been under intense on Anti-Fouling performance investigation for its medicinal benefits. Abstract The structure of curcumin enables tautomerisation, which results in two Responsive surfaces have attracted distinct forms: the diketo and keto- attention largely due to their ability enol tautomers. Recent work has to resist contamination, a property established the link between important for many industrial tautomerisation and the medicinal applications including paint coatings. effects of curcumin. It is well known Recently the bio-contamination of that the keto-enol form of curcumin these surfaces attracted significant 130 www.physchem2013.com.au attention, and Specifically, bio-fouling [3] Paslay, LC, Falgout, L, Savin, DA, by class I Hydrophobins, a family of Heinhorst, S, Cannon, GC & Morgan, SE, small, amphiphilic fungal proteins. Kinetics and Control of Self Assembly of These proteins are best known for ABH1 Hydrophobin from the Edible White Button Mushroom, their ability to self-assemble into Biomacromolecules, 2013, vol. 14, no. 7, stable monolayers, on hydrophobic pp. 2283-93. as well as hydrophilic surfaces[1-2] due to distinct amphipathic [4] Macindoe I., Kwan A., Ren Q., Morris characteristics and can condition V., Yang W., Mackay J., and Sunde M., the surface, regardless of the starting Self-assembly of functional, amphipathic substrate’s polarity and morphology, amyloid monolayers by the fungal thus facilitating further microbial hydrophobin EAS, PNAS Early Edition, 2012, 1-8. growth[3]. [5] Ng, CCA, Ciampi, S, Harper, JB & We present an all-atom molecular Gooding, JJ, Antifouling behaviour dynamics study on the binding of of silicon surfaces modified withself- a class I Hydrophobin, EAS[4], onto assembled monolayers containing both some typical industrial coating ethylene glycol and charged moieties, surfaces modified with poly(ethylene Surface Science, 2010, vol. 604, no. 17-18, glycol) (PEG) chains for potential pp. 1388-94. antifouling protection[5]. We investigate the effects of surface flexibility and PEG coverage density on the interaction between the Poster 50 protein and PEGylated substrates, as well as the evolution of the secondary Cassandra Lutzko, Maoyan Liu, Angus Gray-Weale and tertiary structure of the protein The University of Melbourne during adsorption. Results show that PEG modifications of the surfaces Free Energy of Solvation for induce an increase in Hydrophobin mobility and perturb the secondary a Uranium ion in the LiCl-KCl structure of the protein. Eutectic

References Abstract [1] Qin, M., Wang, L.K., Feng, X.Z., Yang, Molecular dynamics simulations of Y.L., Wang, R., Wang, C., Yu, L., Shao, B., the LiCl-KCl eutectic containing a Qiao, M.Q., Bioactive surface modification uranium ion are studied to obtain of mica and poly(dimethylsiloxane) with the free energy of solvation. As hydrophobins for protein immobilization. opposed to current trends, our Langmuir 2007, 23, 4465–4471. method involves the use of classical [2] Zhao, Z.-X., Qiao, M.-Q., Yin, F., Shao, mechanics to calculate the solvation B., Wu, B.-Y., Wang, Y.-Y., Wang, X.-S., Qin, thermodynamics. Our technique X., Li, S., Yu, L., Chen, Q., Amperometric uses a three-step model for the glucose biosensorbased on self-assembly simulations. The first step involves hydrophobin with high efficiency of thermodynamically integrating the enzyme utilization. Biosens Bioelectron. uranium ion from U3+ to U4+ to obtain 2007, 22, 3021–3027. a free energy of solvation for the oxidation reaction. The second step involves using the Widom 131 www.physchem2013.com.au Insertion method to insert a neutral Poster 51 chlorine atom in various locations throughout the eutectic and thus Rowan MacQueen, Yuen Yap Cheng, obtain a chemical potential for the Timothy Schmidt insertion. The third step involves The University of Sydney using thermodynamic integration for reducing the chlorine atom from Cl0 Nanostructured Upconverters to Cl- to obtain the free energy of for Solar Energy Applications solvation for the reaction. Currently simulations have been done for the Abstract temperatures 800K to 2000K. The energy conversion efficiency of quantum solar energy collectors is limited by a mismatch between the step-like nature of the band gap and the continuous energy distribution of sunlight. Photon upconversion is one approach to overcome this, where photons with energies insufficient to cause excitation across the band gap have their energies combined, yielding upconverted light that can be absorbed by the collector Using triplet-triplet annihilation upconversion (TTA-UC), which exploits the strong broadband absorption of molecular chromophores, we have measured small but clear improvements in the output of solar cells under low solar concentration (~several suns). TTA- UC is a bimolecular process, so in order to improve the efficiency under one-sun illumination we are working to dramatically increase the chromophore density. This necessitates a move to solid materials, where we use nanostructured scaffolds to support high loadings of chromophores while impeding aggregation-induced quenching. To this end, mono- carboxylic acid tetrakisquinoxalino palladium porphyrin was coupled to silica nanospheres functionalised with aminopropyltrimethoxysilane using peptide coupling chemistry. Kinetic studies of the functionalised silica were carried out, and the results

132 www.physchem2013.com.au compared to free dye solutions pre-resonance with the Soret band at equivalent concentration. The and Q band, respectively. phosphorescence lifetime of the dye was longer when tethered than High-resolution Raman imaging of in solution, suggesting a disruption thin smears of whole blood shows of aggregation. Quenching of the the existence of a thin outer layer porphyrin sensitiser by rubrene emitter of haemoglobin in RBCs, where the was slightly slower in the tethered Fe3+ state of the haem dominates. system, likely due to hindered The Fe3+ layer may protect the diffusion. The output of an amorphous internal parts of RBCs from oxidation. silicon solar cell was enhanced by Such behaviour of RBCs may also the tethered upconverter system, but suggest that in air-dried blood unremarkably so. We are working to preparations haemichrome is improve the dye loading and kinetic created on the outer surface of RBCs, parameters of the tethered-dye while haemochrome resides inside TTA-UC system. Initial challenges and the cells. The interactions with blood results from this venture are plasma show that carotenoids may reported. have an impact on the oxidative processes in RBCs. Moreover, it was possible to observe the oxidation of the haem iron in situ of RBCs treated with different external oxidants and Poster 52 reductants. To fully understand and evaluate the results obtained from K.M. Marzec1, M. De Veij2, D. Pérez Guaita2, B. R. Wood2, thin smears, the measurements of S. Chlopicki1, M. Baranska2 functional RBCs in buffered solutions are compared 1. Jagiellonian University, Krakow, Poland, 2. Monash University, Melbourne, Australia Acknowledgement: This work was supported by the European In situ High-Resolution Raman Union under the European Regional Development Fund (grant coordinated Imaging of Erythrocytes from by JCET-UJ, POIG.01.01.02-00-069/09) and Whole Blood Go8 European Fellowship.

Abstract In the presented studies, red blood cells (RBCs) from whole blood were studied using confocal Raman microscopy. High-resolution Raman imaging of the RBCs in thin smears of whole blood as well as RBCs in buffered solutions enabled us to obtain spatial information on the oxidation states of haemoglobin (Hb) inside the cells. The excitation of RBCs using 488 nm and 532 nm laser gave an enhancement of Raman signal of the Hb chromophore through the 133 www.physchem2013.com.au Poster 53

Laura K. McKemmish, Dr Andrew T. Gilbert, Prof Peter M. W. Gill Australian National University

Ramps: A new type of basis function for faster quantum chemistry calculations

Abstract Gaussian basis sets are ubiquitous in computational chemistry due to their unparalleled mathematical properties. However, Gaussians have no cusps and their use is an inefficient way to model the cusp and core region of real orbitals; this leads to a undesirably large number of Gaussians in conventional basis sets Fig. 1 (a) Microphotographs of the (a) to describe the core region, which is fresh human RBCs (full blood, smear on generally chemically unimportant. the CaF2 slide) with the labeled (red) We propose the introduction of a investigated area; (b): Integration maps new type of basis function, namely a of Hb bands in the spectral region of 1350-1380 cm-1 (ν4, for 488 nm laser ramp, which has the basic form: wavelength); (c): The K-means Clustering (KMC) results with the 3 main classes of dominance of Hb Fe3+ (blue), Hb Fe2+ (red) and partially deoxygenated Fe3+/2+ (green). The spatial resolution was equal Ramps have cusps at the origin, to 0.33 μm. The average spectra of the but decay entirely at 1 bohr. This respective 3 classes from the K-means allows many of the new integrals Clustering (KMC) were obtained with the use of laser wavelengths of 488 nm and involving ramp basis functions to 532 nm (spectral resolution of 3 cm-1). be calculated via interaction of the multipole moments or even neglected entirely, in stark contrast to the difficulty of calculating integrals involving the cusped Slater functions that were historically used before the introduction of Gaussian basis sets. Modelling non-concentric ramp-Gaussian shell pairs as a sum of ramps further simplifies two- electron integrals because this means that only two-center integrals are required, as is the case for two- electron integrals using Gaussian- only basis sets after application of 134 www.physchem2013.com.au the Gaussian product rule and Boys Poster 54 differentiation. Efficient basis sets can be formulated by combining Grant McKenzie, Anita C. Jones localized ramp functions, for the Joseph Black Building, King’s Buildings, treatment of nuclear-electron cusps, Edinburgh with Gaussians, for the intermediate and valence regions. These mixed Using 2-Aminopurine to Study ramp-Gaussian basis sets have far Excitation Energy Transfer in fewer primitive basis functions than the standard Gaussian basis sets. DNA As integral evaluation and code Abstract development for these new classes of integrals is optimised in the future, Transfer of excitation energy these smaller mixed basis sets between DNA bases and the may have the potential for faster fluorescent, modified adenine base calculations without limiting the 2-aminopurine (2AP) has been shown ability of the basis set to describe to occur by using 2AP as an energy the chemically important valence acceptor in 2AP-containing region. With this methodology, we dinucleotides and by exciting at develop a preliminary efficient wavelengths in the region where Fortran implementation for Hartree the 2AP absorbance is minimal Fock calculations involving a (approximately 260 nm). 2AP mixed ramp Gaussian basis set. In emission has been observed at the conventional notation, this involves characteristic wavelength of 370 nm the replacement of the “6” in the when the dinucleotide samples are 6-31+G basis set by a “R” (1 ramp and excited at 260 nm which suggests that 1 Gaussian) along with calculation excitation energy transfer is occurring of all required integral types between the donor DNA base and Consequently, we present results for the acceptor 2AP base. Energy small molecules to demonstrate that transfer efficiencies were calculated these mixed basis sets reproduce the from absorption and fluorescence chemistry of their parent basis set. spectra at room temperature it has been found that energy transfer efficiency is only significant in the case of adenine acting as the donor base while in the cases of cytosine, guanine and thymine acting as the donor bases, the energy transfer efficiency is minimal. By freezing the 2AP-containing dinucleotide samples to the low temperature of 77 K, the excitation energy transfer has been shown to greatly increase, thus opening up further work on investigating the fluorescent decay properties of 2AP-containing DNA when excited at 260 nm.

135 www.physchem2013.com.au Poster 55 planar mirror and a spherical curved mirror (R=2 m). The molecule source Dr Chris Medcraft 1, 2, Dr Thomas Betz 1, 2, is a pulsed valve that creates a Dr Melanie Schnell 1, 2, 3 supersonic expansion, which enters the resonator through the centre of 1. Max Planck Institute of the Structure and the planar mirror. The electronics Dynamics of Matter, Hamburg, Germany, consist of a 0-20 GHz analogue signal 2. Center for Free-Electron Laser Science, generator (3 in figure 1). A frequency Hamburg, Germany, doubler increases the spectral range 3. Center for Ultrafast Imagining, Universität Hamburg, Hamburg Germany to 40 GHz. This signal is mixed with a 30 MHz carrier frequency (5) and then coupled to the cavity. The A new semi-confocal high- molecular response is amplified (11) resolution FTMW spectrometer and measured by a 12.5 GS/s digitiser (1). The resolution is expected to on Abstract the order of 3 kHz, limited by transit- A high-resolution, cavity-based, time and Doppler broadening. This Fourier-transform microwave instrument will allow investigations spectrometer is being commissioned of nuclear quadrapole hyperfine in Hamburg. The spectrometer is structure, internal rotations and, in based around the COBRA design combination with a source of cold, (Coaxially Oriented Beam Resonator slow molecules, chirality effects. Arrangement [1]). It consists of a semi-confocal arrangement of a [1] Grabow, Rev. Sci. Instrum.67, 4072 (1996)

Figure 1: Scheme and block diagram of the electronic setup of the new semi- confocal FTMW spectrometer.

136 www.physchem2013.com.au Poster 56

Michael Morris, A/Prof Meredith Jordan The University of Sydney

Building Dipole Moment Surfaces with Modified Shepard Interpolation

Abstract An essential component required Figure 1. The DMS of ClH:NH3 as a function for the prediction of rotation- of its Cl–H and N–H bond lengths. vibration spectral line intensities is the [1] Morris, M.; Jordan, M. J. T. J. Chem. molecular dipole moment surface Phys. 2013, 138, 054111/1–9. (DMS). Knowledge of the DMS can also be used to predict the first [2] Collins, M. A. Theor. Chem. Acc. 2002, order response of a molecule to an 108, 313–324. external electric field,1 as well as the experimental dipole moment, (ψ_0 |μ| ψ_0). Poster 57 In practice, DMSs are often constructed using functional forms fit Dr Klaas Nauta, Nicholas Hobday, to ab initio or experimental data. Mitchell Quinn, Gaby de Wit, Duncan Constructing an accurate DMS in this Andrews, A/Prof Meredith Jordan, manner, however, can be difficult Prof Scott Kable due to fitting errors and errors arising University of Sydney from the nature of the functional form used. Even when a large Triple-fragmentation of number of parameters are used in Formaldehyde: using Velocity conjunction with high-level ab initio Map Imaging and 2D REMPI and experiment data, problems can persist. In light of such difficulties, it to determine complete is worthwhile to consider alternative photochemical quantum yields methods for the generation of accurate DMSs. We investigate Abstract whether the modified Shepard Formaldehyde, H2CO, is a well- interpolation scheme of Collins and studied molecule where its co-workers2 is a viable alternative photochemistry is concerned. The for building accurate DMSs using the S0-S1 absorption spectrum covers water molecule as a test species. a range of ~28,000 cm-1 to 40,000 Some applications of this scheme are cm-1, with discrete vibronic structure also considered. up to approximately 38,000 cm- 1. Within that range a variety of photochemical processes can occur. These are listed below with their approximate energetic thresholds.

137 www.physchem2013.com.au The first four processes have been well studied, both experimentally and theoretically and are reasonably well understood. The fifth process, triple-fragmentation, was recently Poster 58 investigated by us using Velocity Map Nina Novikova, A/Prof Cather Simpson, Imaging. Prof Penelope Brothers The University of Auckland With the VMI apparatus we have looked at the velocity distributions of Spectroscopic investigation of nascent hydrogen atoms as well as rotationally resolved CO fragments as boron porphyrin/porphyrinoid a function of photolysis energy across complexes the entire S1-S0 absorption spectrum. With hydrogen atoms, the velocity Abstract distributions show a clear signature Porphyrin complexes of transition of triple-fragmentation at photolysis metals and many main group energies above ~ 36,000 cm-1, while elements have been extensively the distributions also allow us to studied in the past years due to the distinguish hydrogen atoms formed in important roles they play in many reactions R3 and R4. biological processes. The number of new applications for porphyrin Rovibrationally resolved, 2D VMI- compounds is increasing continuously REMPI scans of the CO fragment in such fields as medicine, allow us to separate out fragments photovoltaic devices, biological formed in reactions R1, R2 and imaging, polymer materials and R5. Together, the H-atom and CO oxygen sensing. With this driving the distributions form a complete picture research and with advancements of the photochemical fate of S1- in analytical techniques, a more excited formaldehyde and allow us in-depth examination of porphyrin to extrapolate quantitative branching complexes with semi- and non- fractions for all photochemical metallic elements is underway.1 products. Combined with published Boron porphyrins and boron total quantum yields for the CO and porphyrinoids in particular are HCO fragments, we can try to infer attractive candidates for a wide the quantum yields for each of the range of potential applications due reactions R1-R5 at a wide range of to their unique structural features, excitation energies. surprising versatility and unusual 138 www.physchem2013.com.au chemical reactivity.2 The most distinctive feature exhibited by boron porphyrin complexes is coordination of two boron atoms within the cavity of porphyrin macrocycle, where each boron atom is coordinated to two nitrogen atoms. This results in a large tetragonal elongation of the porphyrin ring along the B-B axis.3 The similarity in structure of some of the boron-porphyrin complexes to the BODIPY dyes used in fluorescent labelling is another feature that offers intriguing potential for the application of these complexes. To examine this possibility, spectroscopic analyses of boron- porphyrin complexes, synthesised by previously reported methods,1,2 have been carried out using femtosecond transient absorption spectroscopy, fluorescence, IR and Raman spectroscopy as well as DFT calculations. Transient absorption spectroscopy was used to study the dynamics of the transient species by exciting the molecule with a ~100 fs pulse of light at the wavelength corresponding to the Soret and Q band absorptions of those complexes and recording a UV/Vis absorption spectrum at a series of time delays after the excitation. The results from this study will be presented and discussed.

References [1] Belcher, W. J.; Boyd, P. D. W.; Brothers, P. J.; Liddell, M. J.; Rickard, J. Am. Chem. Soc. 1994, 116, 8416-8417.

[2] Weiss, A.; Hodgson, M. C.; Boyd, P. D. W.; Siebert, W.; Brothers, P. J., Chem. -Eur. J. 2007, 13, 5982-5993.

[3] Brothers, P. J., Chem. Commun. 2008, 2090-2102.

139 www.physchem2013.com.au Poster 59 Poster 60

Gerard O'Connor, Dr George Bacskay, Adabelle Ong1,2, Benjamin Morrison1,2, Gabrielle Woodhouse, Dr Tyler Troy, Clare Henderson1,2, Trevor Smith1,2 Dr Klaas Nauta, Prof Scott Kable, A/Prof Timothy Schmidt 1. The University of Melbourne, The University of Sydney 2. ARC Centre of Excellence for Coherent X-ray Science Jet-Cooled Excitation Spectra of Large Benzannulated Benzyl Self-Assembled Nanostructures Radicals: 9- anthracenylmethyl for High Resolution (C15H11) and 1-pyrenylmethyl Characterisation

(C17H11) Abstract

Abstract Self-assembled ordered arrays of mono and binary colloidal systems The jet-cooled D1 ← D0 excitation comprising micro- and nanometre- spectra of two benzannulated benzyl sized spheres can form patterned radicals (BBRs), 9-anthracenylmethyl nano-structures. These have the (9-AnMe) and 1-pyrenylmethyl (9- potential to be used in many PyMe), have been obtained using applications including photonic mass-resolved resonant two-colour bandgap devices, chemical two-photon ionization spectroscopy sensors, biosensors and biomaterials (R2C2PI). Analysis of the spectra in templates. Self-assembled patterned view of symmetry and calculated nano-structures also provide vibrational frequencies indicate excellent test samples for new high- significant vibronic coupling. resolution X-ray/extreme ultraviolet From the spectrum of 9-AnMe we (XUV) coherent diffraction imaging elucidate significant anharmonicity in (CDI) and super-resolution optical the excited state. imaging methods. CDI allows images to be reconstructed from X-ray/XUV This anharmonic behaviour is diffraction patterns of a sample, and examined computationally through optical imaging methods can provide both TDDFT and ab initio methods. comparable and complementary Excited state properties of 9-AnMe information if one or both of the and 1-PyMe are examined with binary colloids fluoresces. reference to the existing spectra of smaller BBRs. Trends in the observed In this work we have generated spectra of BBRs allow spectroscopic binary colloidal arrays of fluorescent properties of larger BBRs to be and non-fluorescent particles on predicted. These predictions suggest silica and silicon nitride substrates. the D1 ← D0 transitions of large BBRs These arrays have been imaged are unlikely to be carriers of the with both XUV CDI in order to diffuse interstellar bands. characterise the algorithms for the CDI reconstruction process, and structured illumination (SIM) and stimulated emission depletion (STED) microscopy. Each sample exhibits

140 www.physchem2013.com.au controllable morphological features or order and disorder on the micro- to nanometre scale. Preliminary CDI experiments using an ultrafast laser based high harmonic generation source confirm that these ordered arrays show promise as test samples for this emerging technique. In Scheme 1 addition, with the use of fluorescent spheres, we are able to demonstrate The experimental apparatus employs time-resolved fluorescence lifetime a reactor flow tube coupled with imaging and characterise a range of kinetically resolved photoionisation super resolution microscopy methods. mass spectrometry. Radical reactions initiated by photolysis in the presence of O2 (298 K, 4 Torr) are probed using tunable synchrotron radiation (Advanced Light Source, LBNL) and Poster 61 time-of-fight mass spectrometry, with isomer specificity afforded by Matthew B. Prendergast1, photoionisation spectra. Quantum Benjamin B. Kirk1, Stephen J. Blanksby1, Gabriel da Silva2, Adam J. Trevitt1 chemical calculations and RRKM/ Master Equation modelling are 1. University of Wollongong, utilised to provide additional insight 2. The University of Melbourne into the oxidation mechanisms and rationalise observed reaction Product Branching Studies of products. ortho-Substituted Phenyl + O2 Scheme 2 depicts the dominant Reactions: Experimental and reaction pathways predicted for Theory 2-hydroxylphenyl + O2. Similar to phenyl + O2, pathways A and B are Abstract accessible. The study of aryl-radical + O2 reactions is fundamental to understanding combustion chemistry as aromatic hydrocarbons comprise a large fraction of transportation fuels. To comprehend the function of aromatic fuel additives in combustion, and tune performance, Scheme 2 detailed molecular understanding of aryl-oxidation is essential. In this The new pathway, C, afforded presentation we describe the by the proximity of the hydroxyl- experimental and theoretical hydrogen, allows for ROO → QOOH investigation of ortho-substituted isomerization and subsequent phenyl + O2 reactions shown in OH elimination to produce Scheme 1. 1,2-benzoquinone. The benzoquinone species, implicated in coal and wood combustion, undergoes 141 www.physchem2013.com.au CO elimination to produce S. Rudolph, V. Staemmler, and M. cyclopentadienone. ortho Havenith, Phys. Rev. Lett. 95, 215301 Substitution of phenyl radicals opens (2005)]. A simple model is presented up new chemistry and reaction that predicts the observed Λ-doublet products in aryl-radical + O2 splittings in helium solvated OH and reactions relevant to combustion. NO. The model assumes a small parity dependence of the rotor's effective moment of inertia and predicts a factor of 3.6 increase in the OH ground state (J=3/2) Poster 62 Λ-doubling when the B0 e and B0 f rotational constants differ by less Paul Raston1, Tao Liang2, Emmanuel Obi2, Gary Douberly2 than one percent. Other species probed include the linear OH-CO 1. The University of Adelaide, complex, for which we searched for 2. University of Georgia the weakly bound, higher energy, OH-OC structural isomer, but to no Helium Nanodroplet Isolation avail., suggesting that it is either Spectroscopy of the Hydroxyl relatively unstable with respect to isomerization, or that the long-range Radical and of its Complexes interactions in helium nanodroplets with Carbon Monoxide and guide the molecules to the global Methane minimum (OH-CO) on the associated potential energy surface. The OD-CO Abstract complex was also investigated with The hydroxyl radical and its the hope that the lower zero-point complexes with carbon monoxide energy might stabilize the higher and methane have been energy isomer. Stark spectroscopy characterized in cold (0.4 K) helium was performed on this important nanodroplets by infrared depletion atmospheric complex, and its analysis spectroscopy. For OH and OD, two shall be presented at the meeting. sharp Q branch lines were observed, Addition of CH4 to OH doped helium with a separation that indicates a droplets results in the formation of large increase in the Λ-type doubling the rather floppy OH-CH4 complex in helium nanodroplets (relative to the which has a very rich rotationally gas phase). From an analysis of the resolved spectrum. Measurements of Stark spectrum of the Q(3/2) branch deuterated complexes have been transitions of OH, the Λ-doublet made (OD-CH4, OH-CD4, and OD- splittings are determined to be 0.198 CD4), the relative line widths of which cm-1 and 0.369 cm-1 in the ground provide information about the flow of and first excited vibrational states, vibrational energy in the complexes, respectively. These splittings are and the line spacings and relative 3.6 and 7.2 times larger than their intensities of which provide clues as respective gas phase values. A to the spectroscopic assignment and factor of 1.6 increase in the Q(1/2) equilibrium structure. Λ-doublet splitting was previously reported for the helium solvated NO radical [K. von Haeften, A. Metzelthin,

142 www.physchem2013.com.au Poster 63 neutral species5 and ionic liquids.2 Therefore, SCS-MP2 can provide a Jason Rigby, Dr Ekaterina Izgorodina route by which CP correction could Monash University be avoided. In this study, we expand upon this by presenting a refined New spin-component set of SCS-MP2 scaling factors for the parallel and antiparallel spin scaled MP2 coefficients to components, as well as for the approximate CCSD(T) for scaled opposite-spin MP2 (SOS- charged systems MP2)6 variant, determined by multivariate least squares regression Abstract analysis. The spin components of Accurate electronic structure 17 popular basis sets are fitted to calculations of charged species is a counterpoise corrected CCSD(T)/ challenging aspect of computational CBS interaction energies of a wide chemistry, particularly when charge range of ionic liquids including a transfer and dispersion forces are variety of energetically accessible significant. Density Functional Theory, conformations and validated against in most cases, has shown to be the S66/S22 datasets7, 8 as well as poorly suited to the task1, 2, both in several charge transfer complexes. terms of the charges themselves and We demonstrate that while SCS- accurate dispersion energies. We MP2 methods are sensitive to the therefore must resort to fully ab initio choice of basis set, remarkable correlated methods in order to best agreement with CCSD(T) energies account for these interactions. Highly below spectroscopic accuracy can accurate methods, such as Coupled be achieved while avoiding costly CP Cluster theory, show poor scalability correction. with molecular size and are typically limited to small molecular systems. [1] E. I. Izgorodina, U. L. Bernard and D. R. MacFarlane, J. Phys. Chem. A, 2009, 113, An additional bottleneck arises from 7064-7072. basis set superposition errors (BSSE) which is usually corrected via the [2] S. Zahn, D. R. MacFarlane and E. I. counterpoise (CP) correction scheme Izgorodina, PCCP, 2013, 15, 13664-13675. by Boys and Bernardi.3 The CP correction scheme requires a number [3] S. F. Boys and F. Bernardi, Mol. Phys., 1970, 19, 553-566. of time-consuming calculations, which becomes non-trivial for larger [4] S. Grimme, J. Chem. Phys., 2003, 118, clusters. Recently our group has 9095-9102. shown that for charged systems such as ionic liquids, CP correction [5] J. Antony and S. Grimme, J. Phys. Chem. A, 2007, 111, 4862-4868. was necessary to closely reproduce CCSD(T)/CBS interaction energies.2 [6] Y. Jung, R. C. Lochan, A. D. Dutoi and Spin-component scaled MP2 M. Head-Gordon, J. Chem. Phys., 2004, (SCS-MP2)4 has been shown to 121, 9793-9802. significantly improve energies [7] P. Jurecka, J. Sponer, J. Cerny and P. with respect to high-level CCSD(T) Hobza, PCCP, 2006, 8, 1985-1993. calculations which, when coupled with a triple-ξ basis set, exhibited a [8] J. Rezac, K. E. Riley and P. Hobza, J. fortuitous cancellation of errors for Chem. Theory Comput., 2011, 7, 2427-2438. 143 www.physchem2013.com.au Poster 64

Cameron Ritchie, Dr Angus Gray-Weale The University of Melbourne

Permanent Dipole Correlations Drive Self-Assembly in Various Solvents

Abstract A simple theoretical model for self- assembly consisting of a combination of permanent dipole correlations and a Debye-Hückel approximation was employed to calculate properties of micellation such as the cmc and aggregation number of surfactants. The driving force for micelle formation is described by a series of competing solvophobic, solvophilic and electrostatic steps. We build upon Figure: Thermodynamic steps which previous work by Chandler et al.3 contribute to micellation and Klein et al.4 by describing solvent effects with permanent dipole correlations which provides a model for self assembly capable of Poster 65 predicting all known dependences of micelle formation and micellar Patrick Robertson, Isabella Lobo, properties. The theory is validated Dr Evan Robertson, Dr David Wilson against experimental data for both La Trobe Institute of Molecular Science ionic and non-ionic surfactants in a number of different solvents. The Conformational analysis of theoretical calculation of size, salt and temperature dependence of biomolecules in the gas-phase ionic and non-ionic micellation, and by optical spectroscopy? Don’t a solvent’s capacity for self-assembly amide if I do all agree with experiment. This model allows for calculations of properties Abstract of self-assembly where cmc Conformational analysis of computations become infeasible. neurotransmitter and other Applications of this theory include biologically important molecules prediction of new solvents capable and their analogues has significant of supporting self-assembly, and implications in understanding their manipulation of micellar properties biological activity, pharmaceutical to promote desired nano and micro design and fundamental character. scale structures. A number of optical spectroscopic techniques have been used to determine the conformational 144 www.physchem2013.com.au preferences of a variety of exciton and charge dynamics in biologically relevant molecules ordered, interconnected poly(3- in the gas phase. Resonance hexylthiophene) (P3HT) nanofibres1,2 enhanced multi-photon ionisation using femtosecond transient spectroscopy (REMPI), UV-UV and absorption spectroscopy. The IR-UV hole burning have identified high-energy excited states of P3HT and assigned a number of unique nanofibres in anisole were studied via conformers present in jet-cooled two-pulse/ pump-probe and expansions of 4-vinyl imidazole and three-pulse/ pump-repump- phenelzine. Comparison of spectral probe techniques. The excited- data to ab initio and DFT calculations state absorption spectra (Figure has assisted in the assignment of 1) obtained from the pump-probe conformational preferences in each experiment exhibit a broad photo- compound. induced absorption band in the near IR region (approx. 850 to 1450 nm) 3. The red shift of this absorption band over time indicates the decrease in the energy of singlet Poster 66 excitons. The pump-repump-probe experiment involved generating an Charu Rohatgi The University of Adelaide exciton population with first laser pulse and then re-pumping these excitons with a second near IR laser Near-IR Femtosecond Transient pulse to promote them to highly Absorption Spectroscopy excited states. The results suggest of Poly(3-hexylthiophene) that re-pumping the excitons leads Nanofibres to exciton dissociation to yield free charge carriers. Abstract References Exciton generation and charge [1] Samitsu, S.; Shimomura, T.; Heike, S.; recombination play a major role Hashizume, T.; Ito, K. Macromolecules in determining the efficiency of an 2008, 41, 8000. organic solar cell. The investigation into exciton and charge dynamics [2] Schwarz, K. N.; Kee, T. W.; Huang, D. M. is therefore an important step Nanoscale 2013, 5, 2017. towards understanding the ultra- fast photovoltaic conversion. This [3] Clafton, S. N.; Huang, D. M.; Massey, research aims to investigate the W. R.; Kee, T. W. J. Phys. Chem. B 2013, 117, 4626.

Figure 1: Excited state absorption spectra for P3HT nanofibres in anisole excited at 400 nm and chemical structure of poly(3- hexylthiophene) (P3HT).

145 www.physchem2013.com.au Poster 67 from a tunable laser. Electronic excitation of the molecular cation Julian Sanelli, Dr Nahid Chalyavi, Dr can lead to rupture of the weak Viktoras Dryza, Prof Evan Bieske intermolecular bond and release of the University of Melbourne the rare gas atom following either internal conversion from the excited Electronic Spectroscopy electronic state or fluorescence of Cyclic Hydrocarbon to a vibrationally excited level in the ground state. The cation Cations in the Gas Phase photofragment is mass-selected with using Resonance-Enhanced a second quadrupole mass filter and Photodissociation passed through to the ion detector. An absorption spectrum is produced Abstract by monitoring the photofragment Hydrocarbon ions are believed to signal as a function of excitation play an important role in combustion wavelength. chemistry, where they are found as reactive intermediates in the Molecular species studied using formation of aromatic rings, and in this approach include radical interstellar chemistry, where they cations (e.g., indene+, indole+, are considered as candidates for and cyclopentadiene+) and carriers of absorption features in closed-shell protonated cations the interstellar medium. Despite (indeneH+ and pyridineH+). The persistent efforts, there still exist many technique also allows the effects of fundamental cyclic and polycyclic microsolvation on the ion’s electronic hydrocarbon ions that have escaped transitions to be examined. For spectroscopic characterisation in the example, in the case of pyridineH+, gas phase. Examining molecular ions we have investigated the effect in isolation, free from the perturbing of microsolvation by H2, N2, H20 effects of solvent or matrix, is essential and NH3 molecules. Experimental for a rigorous understanding of their observations are compared with intrinsic structure and energetics. theoretical predictions made using We have recently recorded the time-dependent density functional electronic spectra of several cyclic theory (TD-DFT). Ground and excited hydrocarbon cations in the gas state geometry optimisations phase, employing resonance- and vibrational frequencies are enhanced photodissociation calculated with the B3LYP functional spectroscopy in conjunction with and cc-pVDZ basis set, allowing tandem mass spectrometry. The theoretical simulation of the vibronic molecular cations are generated spectrum and assignment of Franck- by electron impact on a supersonic Condon active vibrational modes. expansion seeded with vapour from a suitable precursor. In most cases, the cations are ‘tagged’ with a weakly- bound rare-gas atom (He or Ar). The parent ion complexes are initially mass-selected using a quadrupole mass filter, then exposed to light

146 www.physchem2013.com.au modelled accurately using single reference methods and can proceed by concerted, asynchronous biradical or stepwise biradical transition states, as observed in the iso-electronic butadiene dimerisation system. This research aims to use MCSCF methods to determine the preferred reaction pathway and the effect of dynamic correlation on the calculated MCSCF energies. The first systematic study of the influence of active space and basis set size on the butadiene dimerisation Figure 1: Vibrationally resolved D2¬D0 and butadiene-ethene reaction is electronic transition of indole radical performed to act as a benchmark cation. Experimental (top) spectrum of for the methanal azine calculations. He-tagged indole+ in the gas phase; Active spaces include a minimal to simulated spectrum (bottom) from full selection of π orbitals and lone calculated Franck-Condon factors pairs of electrons; encompassing determined using TD-DFT. active spaces of (4, 4) through to (14, 14) where relevant. The basis sets STO-3G, 3-21G, 6-31G(d) and 6-31+G(d) are also used. Here we Poster 68 show that dynamic correlation is vital to providing an accurate model David Scarborough, Christopher of reaction barriers, larger basis Thompson, Ekaterina Izgorodina sets improve MRMP2 results whilst Monash University increasing active space size has little effect, indicating that the inclusion MCSCF models and competing of lone pairs of electrons and all mechanisms of [4π + 2π] π orbitals in the active space may cycloadditions be unnecessary. The performance of single reference methods is also Abstract revisited. Polymeric methanal azine was first synthesised in 1893 and two structures, corresponding to [2π + 2π] and [4π + 2π] cycloadditions, have been proposed. Previous (unpublished) work suggests that there is a preference for the [4π + 2π] cycloaddition mechanism and therefore the polymerisation by this route has been modelled to predict reaction energies and barriers. Computational studies indicate that cycloaddition reactions cannot be

147 www.physchem2013.com.au Poster 69 clusters, and the interactions of the clusters. Post-synthesis treatments Kathryn Schroeder, Jason Alvino, involved calcination under pure O2 Trystan Bennett, Gregory Meth atmosphere at 200 °C for 2 h and The University of Adelaide calcination under pure O2 at 200 °C for 2 h followed by calcination in Photocatalysis of CO2 and H2O H2 at 200 °C for 2 h7,8. Gas phase using Aun cluster doped TiO2 photocatalysis experiments were nanoparticles undertaken to test anatase TiO2 nanoparticle catalysts doped with Abstract gold clusters. Powdered catalysts were deposited on discs that were Climate change and decreasing placed in the reaction cell, which fuel reserves have forced the was connected by a pulse nozzle to development of alternative methods an RGA mass spectrometer as part of producing energy. One area of a vacuum system. Water vapour is conversion of solar energy into (~18 Torr) was allowed into the cell chemical bonds, which allows the and then Ar (for water splitting energy to be easily stored. These experiments) or CO2 (for CO2 reactions do not readily occur. reduction experiments) was pulsed Research has been done into into the cell to 300 Torr. The reaction water splitting and CO2 reduction was illuminated with a 365 nm ±5 to methane, methanol or higher nm UV LED light, with an adjustable order hydrocarbons1-3. A catalyst power that has a maximum of ~38 in the form of nanoparticles of the mW illuminating the catalyst disc. The semiconductor TiO2 has been widely reaction was monitored over time studied for their photocatalytic by the RGA mass spectrometer to properties to drive reactions. UV light determine the reaction rate of over is harnessed to excite an electron time. The gold catalysts have shown to the conduction band, leaving ability to split water by producing a valence band hole. The photo- hydrogen. Oxygen production generated electron drives the has not been seen, possibly due reaction of CO2 with protons to to involvement in other reactions. form hydrocarbons and the hole Anatase TiO2 with untreated Au8 drives reactions to split water4-6. To gold clusters is shown in Figure 1 as improve the efficiency of the TiO2 an example of the H2 production. nanoparticles, they can be doped Comparisons have been made to with noble metals, which trap photo- catalysis with Pt/TiO2 in the same excited electrons which reduces system. electron hole recombination. References Gold clusters, which have different (1) Roy, S. C.; Varghese, O. K.; Paulose, M.; properties to bulk gold, were chosen Grimes, C. A. Acs Nano 2010, 4, 1259. as the dopant in this study. The atomically precise Au8, Au9, Au101 (2) Izumi, Y. Coordination Chemistry clusters were chemically synthesised Reviews 2013, 257, 171. and ligand protected. Treatments (3) Yui, T.; Tamaki, Y.; Sekizawa, K.; Ishitani, of the catalysts affect the ligands O. In Photocatalysis; Bignozzi, C. A., Ed.; involved in synthesis of the gold Springer-Verlag Berlin: Berlin, 2011; Vol. 303, p 151. 148 www.physchem2013.com.au Abstract (4) Wang, W. N.; An, W. J.; Ramalingam, B.; Efficient conversion of solar energy Mukherjee, S.; Niedzwiedzki, D. M.; Gangopadhyay, S.; Biswas, P. Journal of to electricity in low-cost organic the American Chemical Society 2012, 134, photovoltaic (OPV) devices requires 11276. the complex interplay between multiple processes and components (5) Mori, K.; Yamashita, H.; Anpo, M. Rsc over various length and time scales. Advances 2012, 2, 3165. Exciton diffusion to the donor- (6) Maeda, K.; Domen, K. Journal of acceptor interface and charge Physical Chemistry Letters 2010, 1, 2655. transport to electrodes (related to (7) Anderson, D. P.; Alvino, J. F.; thin film blend morphology) as well Gentleman, A.; Al Qahtani, H.; Thomsen, as geminate charge recombination L.; Polson, M. I. J.; Metha, G. F.; Golovko, are currently regarded as the V. B.; Andersson, G. G. Physical Chemistry main loss mechanisms limiting Chemical Physics 2013, 15, 3917 device performance. Novel block Semiconducting tri-block copolymer PFM- copolymers including PFM-F8BT-PFM, F8BT-PFM synthesised in-house, have been (8) Anderson, D. P.; Adnan, R.; Alvino, J.; designed to phase separate on the Shipper, O.; Donoeva, B.; Ruzicka, J.-Y.; 20-30 nm scale – a domain size ideal Qahtani, H. A.; Harris, H. H.; Cowie, B.; for maximising exciton collection Aitken, J. B.; Golovko, V. B.; Metha, G. at the donor-acceptor interface. F.; Anderson, G. G. Physical Chemistry Ultrafast transient absorption Chemical Physics 2013, DOI: 10.1039/ c3cp52497c. spectroscopy provides a means of elucidating charge transfer dynamics in a backlog of novel solar cell materials that lack photophysical characterisation. Using a high Poster 70 repetition-rate laser system, polymers are investigated both in solution and Kyra Schwarz, Prof Ken Ghiggino, as bulk heterojunctions in the solid A/Prof Trevor Smith state with spectral and femtosecond The University of Melbourne temporal resolution. This work reveals the means by which these new Transient Absorption materials can lead to smart design to Spectroscopy of Novel overcome current obstacles in OPV Semiconducting Block efficiency. Copolymers for Organic Solar Acknowledgement: We thank Dr David Cells Jones for providing the copolymer sample and ARENA for the provision of a postgraduate scholarship (to KNS) and funding through the Australian Centre for Advanced Photovoltaics.

149 www.physchem2013.com.au Poster 71 Stable reaction products were identified by FTIR spectroscopy, Miranda Shaw1, Alexander Clubb1, revealing the production of primary Balint Sztaray2, David Osborn3, photolysis products: CO and CH4, Meredith Jordan1, Scott Kable1 and secondary products of photolysis to HCO + CH3: CO2, C2H6, H2CO, 1. The University of Sydney, (CH3)2CO, and (CH3CO)2. The primary 2. University of Pacific, USA, phototautomerisation product: 3. Sandia National Laboratory, Livermore vinyl alcohol, VA (CH2=CHOH) was observed at all wavelengths and Phototautomerisation pressures. In addition, the production of Carbonyls to Enols at of 1-propanol (CH3CH2CH2OH) was Atmospheric Pressure of N2 observed, which was attributed to the secondary reaction of VA with Abstract primary CH3 radicals, followed by H The production of enols under addition. atmospheric conditions might have a significant effect on the yield of At 1 atm, the quantum yield for organic acids in the troposphere, VA production increased from the production of which is generally ~1% at 300 nm to a peak of 5% at under-estimated in atmospheric 320 nm, reducing to 1% again at models. For example, vinyl alcohol 330 nm. When the production of (VA) will react facilely with OH 1-propanol is included, the overall radicals and in a couple of phototautomerisation quantum yield subsequent reaction steps produce was as high as 17% at 320 nm and 1 formic acid. atm N2.. In general, ΦVA increased as N2 pressure was lowered, with a Phototautomerisation of common maximum of ΦVA = 23% for irradiation atmospheric carbonyls, such as of 10 Torr of neat CH3CHO at 320 nm. acetaldehyde, has recently been discovered as a likely source of enols. The photolysis quantum yield, Φph Previously, we reported the photo- was determined to be between 5 and 80% depending on pressure tautomerisation quantum yield, ΦVA, and wavelength. Φph was reduced for neat CH3CHO [1]. Here we report with longer wavelength and with ΦVA under atmospherically realistic increased pressure of N2. Our conditions of 1 atm of N2. Quantum yields for photolysis and photo- values of Φph are in broad tautomerisation of acetaldehyde agreement with previously published were measured at a variety of values by Horowitz and Calvert [2] wavelengths (λ= 300 – 330 nm) and and Moortgat and co-workers [3]. pressures (Pacet = 2-20 Torr and PN2 = 0-760 Torr). Photolysis was carried If photo-tautomerization is a general out in a static cell, placed inside an feature of aldehyde and ketone evacuated FTIR spectrometer, using a photochemistry then this mechanism pulsed, frequency-doubled dye laser. may provide the origin of the missing The sample was irradiated at 10 Hz, organic acid yield in atmospheric for 7 minutes, whilst recording the FTIR models. spectrum every 30 seconds.

150 www.physchem2013.com.au References Poster 73 [1] A.E. Clubb, M.J.T. Jordan, S.H. Kable, D.L. Osborn, J. Phys. Chem. Lett., 3, 3522 Dr Matthew Stewart1, (2012) Prof Harry Ridgway2,3, Prof Stephen Gray1, A/Prof Todor Vasiljevic1,4, [2] A. Horowitz, J.G. Calvert, J. Phys. Prof John Orbell1,4 Chem. 86, 3105 (1982). 1. Victoria University, [3] G.K. Moortgat, H. Meyrahn, P. 2. AquaMem Scientific Consultants, New Warneck, Chem. Phys. Chem., 11, 3896 Mexico, USA, (2010). 3. King Abdullah University of Science and Technology, Kingdom of Saudi Arabia, 4. Victoria University

Poster 72 Predicting the outcomes of oxidising processes: The Dr Alessandro Soncini development of a QM/MM The University of Melbourne hybrid simulation method

Vortex magnetic states in Abstract frustrated molecular metal The use of chemical oxidants is a rings: towards single-molecule common feature in the treatment spin torque effects despite the and preparation of drinking water. weak spin- orbit coupling These agents - commonly ozone, chlorine, chlorine dioxide and Abstract chloramines – are utilised for two properties; they have the capacity A theoretical model for sequential to both remove microorganisms (i.e. spin tunnelling through frustrated disinfection) and oxidise organic antiferromagnetic molecular rings in molecules. The ability to oxidise the weak spin-orbit coupling (SOC) organic molecules is an important limit is presented. The metal rings are feature, as this allows for greater shown to support vortex magnetic control of water quality parameters states (toroidal spin states), originating such as taste and odour control, from the interplay between strong as well as removing – or, at least, frustrated exchange interactions and transforming – potentially harmful weak spin-orbit coupling. The model micropollutants which are present predicts that these toroidal states can in many surface waters. Organic be harnessed to exert a spin-torque compounds of particular importance on an input spin-current, inducing are pesticides, endocrine an output spin current with opposite disrupting compounds (EDC’s) and spin-polarization. Thus, the proposed pharmaceuticals and personal model suggests that strong SOC is care products (PPCP’s); all of which not a necessary condition to achieve are commonly found in the surface spin torque and spin accumulation waters that undergo treatment to in molecular devices, as previously produce drinking water. believed.

151 www.physchem2013.com.au However, due to the typically slow calculations of the potentially reaction rates for the oxidation of reactive species, with a molecular these organic compounds, the dose mechanics treatment of the of oxidant (concentration and/ surrounding milieu. This SFMD method or contact time) used in treatment will be detailed here, along with plants is frequently not sufficient some of the initial benchmarking to completely remove all of the work completed using this SFMD potentially harmful EDC and PPCP method to study reactions of molecules from solution, leading to 1,4-dioxane with hydroxyl radicals. the generation of transformation products (TP’s). The TP’s of certain compounds have previously been shown to display enhanced toxicity and/or estrogenicity, compared Poster 74 to the parent compound, which Patrick Tapping, Dr Tak Kee, generally is assumed to be due Dr David Huang to chlorination (in cases where The University of Adelaide a chlorine-based oxidant is applied). Many attempts have Simulation of Energy Transport been made experimentally to determine how partial oxidation in Conjugated Polymer affects the toxicological and/ Systems or endocrinological profiles of selected EDC’s and PPCP’s, as well as Abstract attempting to identify which TP’s are Conjugated polymers are organic produced and, ultimately, responsible semiconductor materials that possess for this change in observed activity. interesting optical and electronic Whilst there have been a number properties and thus have applications of experimental studies that have in organic optoelectronic and successfully identified stable TP’s photovoltaic devices. In a following oxidation, it is unclear conjugated polymer solar cell, whether these products represent the photoexcitation of the polymer full gamut of TP’s, given the wide use produces an exciton – a delocalised of solvent extraction techniques and excited state – that must migrate chromatographic separation analysis; to the donor-acceptor interface techniques which some generated for the energy to be harvested as products may not be suitable for. electricity. The primary mechanism for exciton transport is through a In order to provide further insights into resonance energy transfer process, the potential reactions occurring, where the exciton “hops” between and hence TP’s being produced, spectroscopic units. The efficiency of when organic molecules are partially the migration is heavily dependent oxidised, a novel theoretical method on the morphology of the polymer has been developed and is currently domains, so an accurate simulation under evaluation. This method, which of energy transport therefore requires the team has named ‘Stepped realistic representations of these Forced Molecular Dynamics’ (SFMD), systems. is an iterative method that combines dynamic quantum chemical 152 www.physchem2013.com.au In this research, realistic structures Poster 75 of a polymer commonly used as the electron donor in organic solar cells, Asya Tawfiq1, Dr Graham E. Ball2, poly(3-hexylthiophene) (P3HT), are A/Prof John A. Stride2 generated using a coarse-grained molecular dynamics model, in which 1. University of Wollongong , groups of atoms from an accurate 2. University of New South Wales atomistic model are mapped onto a smaller set of coarse-grained Distance dependent parallel sites. Energy transport through these interactions of graphene with a systems is then simulated using a fully variety of aromatic molecules quantum mechanical model of the exciton. The simulations produce Abstract results that can be directly compared The interaction between aromatic to experimental data, including time species, some containing ring resolved fluorescence, fluorescence nitrogen atoms and substituent anisotropy and steady-state fluorine atoms, with graphene - (6,6) – absorption and fluorescence. an array of 6 x 6 fused aromatic rings of carbon - has been studied using Importantly, the simulations can dispersion corrected density function highlight phenomena that are theory (DFT). The B97X-D/6-31G(d,p) difficult to observe experimentally, functional/basis combination was such as the exciton diffusion employed to probe the interaction pathways and location of “trap” as a function of distance between sites – areas where the exciton the graphene and aromatic species, movement is hindered, reducing the along with the faster semi-empirical efficiency of a solar cell. Ultimately PM6 method for comparison with a these simulations provide detailed lower level, non-dispersion corrected molecular-level insight into energy method. transport mechanisms and how they depend on polymer microstructure, The energetics of the interaction which can potentially be applied between graphene and the aromatic to the rational design of organic molecule when held parallel, that are optoelectronic devices. largely van der Waals’ in nature, was investigated. Beyond a separation corresponding to an energy minimum that was found to be dependent upon the nature of the interacting aromatic species, the interaction becomes increasingly weak with increased separation between the graphene sheet and aromatic species. Significant differences in the energies of interaction were observed when changing the group substituents from hydrogen to a halogen such as fluorine.

153 www.physchem2013.com.au Poster 76 and colour, but notorious for their photolability2, the mechanism Sarah Thompson1,2,5, of which is not well understood. Dr Charles Rohde1, Dr Erin Griffey4,5, Ultrafast transient absorption (TrA) A/Professor Cather Simpson1,2,3,5 spectroscopy has been used to evaluate the response of these 1. The Photon Factory, 2. School of Chemical Sciences, 3. Department of natural anthraquinone chromophores Physics, 4. Department of Art History, to light, in order to probe their 5. The University of Auckland photodegradation timescales and mechanisms. In addition, the Seeing Red: Using relationship between the molecules’ microenvironment and their lifetimes Femtosecond Transient and photodegradation rates has Absorption Spectroscopy to also been examined. The TrA and Investigate Photodegradation photodegradation studies presented in Anthraquinone Dyes and here represent the first femtosecond Pigments time-resolved spectroscopic studies on the majority of these compounds. Abstract They indicate that very small structural differences can have a Anthraquinones are a family of profound impact upon the excited molecules that share a common state lifetimes (and by extension, 9,10-anthraquinone core structure. photodegradation) of these In use since around 2000 BC, 1 chromophores, and show that the anthraquinones remain the second relative rates of photodegradation most industrially synthesised class of in different anthraquinones may dyes, with applications stretching be related to the presence or from their origins as natural artistic absence of free protons/hydrogen pigments and dyes, to synthetic bonding opportunities in their compounds with roles in medicine, microenvironment. In the case of solar energy harvesting, clothing madder, the results demonstrate and food. In almost all of their for the first time the ultrafast applications, both modern and underpinnings of the long-known ancient, it is the anthraquinones’ disparity in the photolability of the interaction with light that makes them two main components of madder: useful, whether as a dye, a pigment, the reported superior macroscopic or a photosensitizer. This interaction photostability of alizarin compared to with light, however, comes purpurin3. with the attendant danger of photodegradation and loss of the This work bridges the fields of art and molecule’s desired function. Nowhere science to work toward a deeper is this more obvious than in the understanding of the fundamental case of the natural anthraquinones interactions that occur between found in historic red pigments; light and molecular structures. Future madder (principally alizarin and work will extend the investigation to purpurin), carmine (carminic acid) cover the molecules’ degradation and lac (principally laccaic acid in the solid state and the possibility A). These anthraquinones were and of photochemical or photophysical are highly valued for their intensity physical reversal of degradation. 154 www.physchem2013.com.au Poster 77

Rhys Tilbury, Ashley Mulder, Michael Wolter, Dr Massiiliano Massi, Prof Mark Buntine Curtin University

Ligand-mediated control of the surface plasmon resonance in metal nanoparticles generated by laser ablation

Abstract Metal nanoparticles were generated by the Laser Ablation Synthesis in Solution (LASiS) approach, encapsulated and stabilised by a variety of ligands in solution. The encapsulation ligands were designed and synthesised to allow the attachment of phosphorescent transition metal complexes on their outer shell, whose distance to the nanoparticle core can be varied to facilitate energy transfer between References the complex-centre excited state [1] Casadio, F.; Leona, M.; Lombardi, J. R.; and the surface plasmon resonance Van Duyne, R. Acc. Chem. Res. 2010, 43, of the core. This exploitation of 782-791. the electronic structure of the nanoparticle surface has insinuations [2] Saunders, D.; Kirby, J. Nat. Gall. Tech. for a variety of photovoltaic Bull. 1994, 15, 79-97. applications.

[3] Clementi, C.; Nowik, W.; Romani, A.; Cibin, F.; Favaro, G. Anal. Chim. Acta. 2007, 596, 46-5

155 www.physchem2013.com.au Poster 78 This poster will describe experiments that probe OH radical kinetics in Bartholomew Vaughn, Phillip Tracey, free-falling water microdroplets. Dr Adam Trevitt Using a precisely timed two laser- The University of Wollongong pulse setup, as shown in Figure 1 (b), radical chemistry is followed by Measuring photo-initiated monitoring a growth in fluorescence radical chemistry in single signal in single microdroplets of water – one at a time – containing known microdroplets concentrations of a profluorescent molecule, terephthalate, and a Abstract hydroxyl radical precursor (H2O2). Aerosol systems are complex OH radicals are liberated in solution chemical environments containing by a UV laser pulse (λ = 266 nm). a range of microparticles/droplets Then a second pulse (λ = 310 nm), that vary in size, shape and timed by a scanned delay, irradiates composition. Particle sizes extend the same droplet exciting the from the nano- to micrometer scale, fluorescent product. The resulting providing an environment rich in fluorescence signal is measured as a surface chemistry arising from the function of delay time thus allowing high ratio between the surface area measurement of the kinetics (Figure 1 and volume. This complicates the (a)). Using this technique the kinetics fundamental study of aerosol as of radical reaction in single droplet there is a mix of homogeneous and are trackable, allowing acquisition heterogeneous chemistry. Studying of second order rate coefficients single microdroplets with controllable allowing comparison with both characteristics provides insight into the bulk system and gas-phase these single-particle processes environments. without obscurement from ensemble averaging.

Figure 1. a) Kinetic plot of experiment data (points) and fitted curve (line) showing production of 3-hydroxy terephthalate. b.) Example of the timed laser pulses irradiating a droplet. 156 www.physchem2013.com.au Poster 79 on the nature of the VL activity of the fluorinated TiO2 photocatalysts is Dr Yun Wang, Dr Haimin Zhang, of a scientific interest and practical Dr Porun Liu, Prof Huijun Zhao importance, although highly Griffith University challenging.

Origin of visible-light activity of In this work, the origin of the VL fluorinated titanium dioxides: A activity for fluorinated TiO2 is confirmed for the first time via DFT study comprehensive theoretical studies. The 3-coordinated surface F atoms Abstract with higher 1s binding energy have Titanium dioxides (TiO2) are been precisely identified to be the VL prominent photocatalysts for activity origin by systematically applications in the clean environment analyzing the 1s core-level shifts and energy fields. Nevertheless, (CLSs) of various types of F atoms the wide bandgap of TiO2-based in the fluorinated TiO2. Further photocatalysts (3.0 - 3.4 eV) has been analyzing the electronic structures one of the major obstacles limiting of the fluorinated TiO2 via semi-local the practical applications of such density functional theory and non- materials because their poor sunlight local hybrid density functional theory utilization capability. Doping methods calculations demonstrate that the are commonly employed to reduce introduction of the surface their bandgap to achieve visible- 3-coordinated F atoms leads to the light (VL) activities. Among all formation of Ti3+ ions in the sub- doping techniques, the fluorination surface that causes the bandgap approach is unique since it does not shrinking, giving a rise for VL introduce any intermediate activity. The results also reveal that energy band, enabling the retention the presence of 3-coordinated of high photocatalytic activity surface F atoms strengthens the of TiO2. The fluorination method adsorption of hydroxyl groups has been widely accepted as an on their vicinity to enhance the effective means to enhance the photocatalytic activity. The findings photocatalytic activity of TiO2- of this work address a long-standing based photocatalysts. Although a scientific question and provide noticeable progress has been made useful guidance for design and on experimental fronts, the origin of development of high performance VL the VL activity of the fluorinated TiO2 photocatalysts. still remains a mystery. On one hand, this could be partially attributed [1] Y. Wang, H. M. Zhang, Y. H. Han, P. to the controversial experimental R. Liu, X. D. Yao and H. J. Zhao, Chem. observations as not all fabricated Comm., 2011, 47, 2829-2831. fluorinated TiO2 photocatalysts are VL active. However, on the other hand, [2] P. R. Liu, Y. Wang, H. M. Zhang, T. C. An, H. G. Yang, Z. Y. Tang, W. P. Cai and H. J. this can be largely due to the lack of Zhao, Small, 2012, 8, 3664-3673. mechanistic understanding on the origin of the bandgap shrinking of [3] Y. Wang, H. M. Zhang, P. R. Liu, T. Sun, the fluorinated TiO2. Therefore, the Y.B. Li, H.G. Yang, X. D. Yao and H. J. Zhao, precise theoretical understanding J. Mater. Chem. A, submitted. 157 www.physchem2013.com.au Poster 80 state surfaces and found new conical intersections which are pending Xindi Wang, Jennifer Stott, characterisation. A/Prof M Cather Simpson University of Auckland

Time-resolved resonance Raman spectroscopy of aryl- diphosphenes

Abstract Recent advances in main group chemistry have spurred increased interest in the synthesis and characterization of heavier main group analogues of carbon compounds. This project builds on the work already done by the Simpson group in identifying the phosphinidene analogue of the nitrene fragment.1 The excited state dynamics of an aryl diphosphene, dmp diphosphene, have been investigated using femtosecond transient absorption (fsTrA) and computationally using the CASSCF method, which have shown the photo-excited S1 and S2 states to be mostly P=P in character. The time-resolved resonance Raman experiment will focus on characterising the short- lived speices that contribute the absorption bands in the 500-650nm region of the S1 and S2 fsTrA spectra with picosecond resolution.1a This will ascertain whether the absorptions observed in the fsTrA spectra belong to the same transient species. At the same time, our group is gaining more Figure 1. (a) Peng, H.-L.; Payton, J. L.; information about the excited state Protasiewicz, J. D.; Simpson, C., P=P potential energy surfaces (PES) Bond Photophysics in an Ar-P=P-Ar using various ab initio techniques Diphosphene. Dalton Transactions including CASSCF//CASPT2 and 2012; (b) Payton, J. L. The photophysical a model diphosphene: diphenyl behaviour of aryl-diphosphenes and diphosphene. We have begun to aryl-phosphaalkenes: a theoretical explore the interactions between study. Case Western Reserve University, the lowest excited state and ground Cleveland, 2010. 158 www.physchem2013.com.au Poster 81 Using off-the-shelf components we have constructed a home-built set- Donna Whelan 1, Aaron Brice 2, up capable of several of these SRFM Dr Gregory Moseley 2, Dr Toby Bell 1 techniques.

1. Monash University, The single-molecule localization 2. Viral Pathogenesis Laboratory, techniques this set-up is capable of Department of Biochemistry and obtain SRFM images by detecting Molecular Biology the emissions of single fluorophores so that the resulting point spread Super-Resolution Fluorescence function distribution Microscopy for Imaging Virally of photons can be solved for the Induced Changes to the Cell precise localization of the emitting Cytoskeleton molecule. Separation of the fluorophores is achieved temporally Abstract by switching the majority of emitters into a temporary dark state and Super-resolution fluorescence only imaging a small number of microscopy (SRFM) allows sub- emitters at any one time. The most diffraction imaging of highly complex straightforward method for achieving nano-structures with a spatial this is called direct stochastic optical resolution of 10-20 nm routinely reconstruction microscopy (dSTORM achieved. The clear advantages (1)) and utilizes high laser flux and of visualizing nanomaterials and a reducing environment to convert cell structures at a spatial resolution fluorophores into a non-emitting a magnitude improved from state. Tens of thousands of images are conventional fluorescence imaging then acquired over several minutes has resulted in a number of SRFM with each image showing a different techniques being introduced subset of fluorophore PSFs. internationally over the past decade.

159 www.physchem2013.com.au Application of SRFM to biologically References relevant questions requires extensive (1) S. van de Linde, A. Loschberger, optimization of conventional T. Klein, M. Heidbreder, S. Wolter, M. immunostaining protocols of the Heilemann and M. Sauer, Nature target molecule as well as of Protocols, 6, (2011), 991. optimization of imaging and buffering parameters. Microtubules (MTs) make (2) K.G. Lieu, A. Brice, L. Wiltzer, B. Hirst, D.A. Jans, D. Blondel and G.W. Moseley, an ideal target as they are polymeric Journal of Virology, (2013) doi: 10/1128/ in nature and well-established as a JVI.00989-13. SRFM benchmarking protein. They have also recently been indicated as a target molecule for the Rabies virus interferon (IFN)-antagonist protein P3. Poster 82 Using conventional biochemical 1 1 methods and diffraction-limited Andy Wong , Prof Don McNaughton , 2 2 microscopy the association of P3 Dr Dominique Appadoo , Ruth Plathe , Dr Evan Robertson3, with MTs and the importance of A/Prof Sigurd Bauerecker4 this association to the lethality and pathogenicity of the virus could be 1. Monash University, deduced (2). The true extent of MT 2. Australian Synchrotron, architectural changes required SRFM. 3. La Trobe University, Wildtype P3 was observed to bundle 4. Technische Universität Braunschweig MTs (diameter=50 nm when stained) and induce unusual curvature Infrared Spectroscopy of (diameter of bundles=100-200 Ethylene Aerosols using nm). An attenuated interferon- Synchrotron Radiation sensitive P3 protein of diminished lethality was observed to have Abstract less bundling with a lower overall average diameter. A singly mutated Ethylene can be readily found in P3 protein (N226-H) with known interstellar media and is one of the impaired MT-association, nuclear many organic molecules formed localization and IFN-antagonistic during photo-chemical reactions function was observed to cause only in Titan’s stratosphere1 – the largest slightly more bundling than in control moon orbiting Saturn. With the cells. These direct observations exception of Signorell et al2, many of sub-diffraction changes to the of the previously reported infrared structure of the MT cytoskeleton give data have been recorded via the previously inaccessible insight into the deposition of ethylene onto a cold role of the P3 protein in Rabies viral surface or through matrix isolation3. infection. Furthermore, these results We present here, mid infrared data of demonstrate a spatial-resolution of ethylene in the aerosol phase using 10-20 nm on our homebuilt SRFM set- Synchrotron radiation. up and the applicability of this new technique to important biological Synchrotron infrared radiation was questions. used to interrogate the physical properties of ethylene particles in the mid infrared region. These 160 www.physchem2013.com.au particles were made using the unique References instrumental setup at the FIR [1] H.G. Roe, I. de Pater, C.P. McKay, beamline at the Australian Seasonal variation in Titan’s stratospheric Synchrotron. The fundamental modes: ethylene (C2H2) observed, Icarus, 169 (2), υ7 (CH2 wag), υ12 (CH2 def), υ11 2004, 440-461. (C-H str) and υ9 (C-H str) were the [2] C.C. Wang, P. Zielke, Ó.F. main focusses of this experiment. Sigurbjörnsson, C.R. Viteri, R. Signorell, Band shapes, wavenumber shifts Infrared Spectra of C2H6, C2H4, C2H2 and and phase transitions were studied CO2 Aerosols Potentially Formed in Titan’s as a function of temperature Atmosphere. change, from 5 -7 K, under varying experimental conditions. [3] E. Rytter, D.M. Gruen, Infrared spectra of matrix isolated and solid Figure 1: A comparison of ethylene ethylene. Formation of ethylene dimers, particles formed at 78.9 ± 0.2 K using 200 Spectrochim Acta, 35A, 1979, 199-207. mbar of He buffer gas and a sample mixture of 1 % ethylene in He.

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