Annual Report 2017 / 2018

Hylleraas Centre for Quantum Molecular Sciences –

The Hylleraas Centre is a Norwegian Centre of Excellence (CoE) shared equally between the University of Oslo (UiO) and UiT The Arctic University of Norway (UiT), with UiO as project owner. It receives an annual funding of 15 million NOK from the Research Council of Norway. In addition, it receives substantial financial support from UiO and UiT. The centre was established on October 1st 2017 for a period of five years with the possibility of an extension for a further five years following a mid-term evaluation.

The Hylleraas Centre is one of 23 national CoEs in Norway. The goal of the CoE program is to stimulate Norwegian research groups to establish larger units focusing on frontier research at a high inter- national level and to raise the quality of Norwegian research.

The Hylleras Centre aims to develop and apply computational methods to understand, interpret, and predict new , physics, and of in complex and extreme environments. It has an extensive visitors program for scientists from around the world, as well as for PhD students and postdocs from other research groups who wish to benefit from the expertise at the centre. Contents

6 8 10 From the From the Board In Brief Directors of Directors 2017/2018 – – –

18 28 30 Research Career Almlöf–Gropen Highlights Development Lectures – – –

34 50 54 Meetings Outreach Ph.D. and Events – Defenses – –

Hylleraas annual report 4 2017 | 2018 56 58 60 Interview with Visitors Externally Visiting Scientist – Funded Projects – –

74 100 106 Research Hylleraas Publications Themes Activity Members – Reports – – 114 Revenue and Expenditure –

Hylleraas annual report 2017 | 2018 5 From the Directors –

From Fringe to Centre Stage

Computation is the third way of a guide, experimental observations may plans for a new Centre of Excellence science – complementing and be misinterpreted, discoveries missed, were developed in 2015 and 2016, supplementing experiment and and opportunities lost. Such experimental targeting complex systems and mat- developments therefore pose new ter–field interactions. On 15 March theory. Simulations are revolu- challenges to computation – we must 2017, we were elated to learn that the tionizing all branches of sciences. develop tools to simulate increasingly Hylleraas Centre was among the ten Over the last decades, computa- complex systems and interpret the new new Centres of Excellence established tional chemistry has moved from observations. At the Hylleraas Centre by the Research Council of Norway for the fringe to the centre stage of of Quantum Molecular Sciences, this the period 2017–2027. chemistry and become a univer- is precisely our vision: The Hylleraas sally adopted tool for exploring Centre will develop and apply computa- As our first annual report demon- the science of molecules and tional methods to understand, interpret, strates, we have made an excellent start and predict new chemistry, physics, and towards realizing our vision. In the first materials. Indeed, it is no longer biology of molecules in complex and 15 months of operation, we published possible to imagine chemistry extreme environments. 81 articles in international journals and without computation. organized several international meet- – The Hylleraas Centre has its origins in ings including the largest congress in the Centre for Theoretical and Compu- theoretical chemistry in 2018 with more tational Chemistry (CTCC), a Centre of than 500 participants. Our members Today, huge resources are being invested Excellence financed by the Research have designed an exhibition on women in new experimental facilities – facilities Council of Norway from 2007 to 2017. in science in Tromsø and organized the that revolutionize the way we study As the CTCC was coming to an end, first Hylleraas Day of popular science matter. Increasingly complex systems we knew exactly what was at stake at Litteraturhuset in Oslo. To fulfil our are being studied at increasingly – a Centre of Excellence is a unique pledge of improved support for young high resolution by embedding them framework for science, education and scientists, we had initiated a career in ultra-fast and ultra-intense photon outreach, allowing us to deepen and development pilot programme (KUPP) environments. The opportunities broaden our scientific activities in ways with participants from eight Centres generated by these developments are that are not possible within individual of Excellence at the University of Oslo enormous. But, without computation as research groups. With this in mind, in the autumn of 2018. We have also

Hylleraas annual report 6 2017 | 2018 had great success in securing external projects, including grants from the Research Council of Norway, NordForsk, and the European Research Council. In 2018, Prof. Odile Eisenstein was awarded the insignes d'officier dans l’ordre de la Légion d'honneur at the Institut de France, while Assoc. Prof. Kathrin Hop- mann was awarded the Gender Equality Prize of UiT The Arctic University of Norway. Congratulations to both!

The premises of the Hylleraas Centre in Tromsø were refurbished in 2017. In Oslo, refurbishment will be completed in June 2019. We are eagerly looking forward to the official opening of the Hylleraas Centre of Quantum Molecular Prof. Trygve Helgaker Prof. Kenneth Ruud Sciences on September 4 and 5 2019 in Director Hylleraas Centre Deputy Director Hylleraas Centre Oslo and Tromsø, respectively. University of Oslo UiT The Arctic University of Norway (Photo: Ansgar Valbø/NORA) We would like to thank the Research Council of Norway for making the Hylleraas Centre a reality and our home institutions for their support during the application process and the first 15 months of operation.

Hylleraas annual report 2017 | 2018 7 From the Board of Directors –

From the Board of Directors

The Board of Directors is impressed We are very pleased to note that the the Hylleraas Centre has taken an with the achievements of the Hylleraas Hylleraas Centre plays an active inter- initiative for improved career develop- Centre for Quantum Molecular Sciences national role in theoretical chemistry, ment of young researchers, (KUPP), in its first 15 months of operation. having already organized a number of and organized in 2018 two workshops Building on the strengths of its prede- meetings and workshops, including with participations of several Centres cessor, the Centre for Theoretical and the largest conference in theoretical of Excellence. Improved career devel- Computional Chemistry (CTCC), the chemistry in 2018, with more than 500 opment will benefit not only the young Hylleraas Centre has continued the participants. Furthermore, two senior but all members of the centre and we tradition of excellence in science, members of the Hylleraas Centre have are following this initiative with great having published more than 80 papers been elected to the Bureau of the interest. in high-quality journals during this International Academy of Quantum short period of operation. In support Molecular Sciences. We would also One concern regarding the first year of its core activities, the members of like to highlight the successful out- of operation at the Hylleraas Centre the centre have secured additional reach activities at the Hylleraas Cen- has been the relatively slow start of external funding, including ToppForsk tre, targeting both students and broad the hiring process. While immediate and Young Research Talent grants audiences in Oslo and Tromsø. hiring is perhaps less critical for a from the Research Council of Norway, Centre of Excellence that follows hard thereby ensuring a sustained high Most of the members of a Centre of on the heels of another centre, we level of activity over the next few Excellence such as the Hylleraas would nevertheless like to see the years, in all six research themes at the Centre are young people — PhD stu- centre be more proactive in hiring new centre. dents, postdocs, and researchers. Their centre members in order to follow the contributions are central to the suc- proposed plans and budget for the cess of the centres. We are glad that centre.

Jo Døhl (chair) Camilla Brekke Atle Jensen Nathalie Reuter Kajsa Ryttberg–Wallgren Head of Department Professor Professor Professor Vice President Dept. Chemistry Dept. Phys. Tech. Dept. Mathematics Dept. Bio. Sciences Vacuum Conveying Division UiO UiT UiO UiB Piab Group, Sweden

Hylleraas annual report 8 2017 | 2018 The Hylleraas Centre will develop and apply computa- tional methods to understand, interpret, and predict new chemistry, physics, and biology of molecules in complex and extreme environments.

Hylleraas annual report 2017 | 2018 9

2017 in Brief –

2017 in Brief

Picture 1: Hylleraas member Dr. Simen Kvaal (Photo Åsmund H. Eikenes/UiO. Licence CC BY 4.0) The Hylleraas Centre began its operations on October 1 2017. This report therefore covers the last three months of 2017. –

Research Outreach and dissemination In December 2017, Titan.uio.no pub- lished an interview with Hylleraas Members of the Hylleraas Centre pub- Together with Prof. Guiseppe Milano member Dr. Simen Kvaal, focusing on lished 18 papers in during the last three at the University of Bologna and Uni- his member­ ship­ of The Young Acad- months of 2017. The most cited paper versity of Salerno, Hylleraas PI Profes- emy of Norway and his interdiscipli- nary research into mathematics, is Enantioselective Incorporation of CO2: sor Michele Cascella published in Status and Potential, published in ACS December 2017 a YouTube video physics, and chemistry within his ERC Catalysis by Hylleraas PI Kathrin Hop- Towards chemically resolved computer Starting Grant BIVAQUM. mann and researcher Ainara Nova and simulations of dynamics and remodelling Picture 1 their coworkers. Most of our papers of biological membrans as an introduc- were published in the area of chemical tion to their eponymous Perspective The publication Connections between physics, the most popular journals being Article in the Journal of Physical Chem- variation principles at the interface of Journal of Chemical Physics and Journal of istry Letters. wave-function and density-functional Chemical Theory and Computation. theories by Hylleraas Director Trygve Helgaker and Hylleraas affiliate Andrew Teal and four co-authors was included in The Journal of Chemical Physics 2017 Editors’ Choice.

Hylleraas annual report 10 2017 | 2018

Picture 2: Hylleraas affiliate Picture 3: The project Molecules in Extreme Environments Asst. Prof. Andy Teale won an at the Centre for Advanced Study 2017–2018 was led by ERC Consolidator grant in 2017. Hylleraas Director Trygve Helgaker (Illustration Camilla Kottum Elmar)

External projects and funding. In December 2017, Hylleraas members In November 2017, Hylleraas affiliate Kathrin Hopmann and Ainara Nova Asst. Professor Andrew Teale won an learned that their NordForsk Univer- ERC Consolidator Grant for the project sity Hub Grant Nordic Consortium for A topological approach to corre- CO2 Conversion had been funded by 21 lation in density-functional theories. MNOK. The consortium, which is led Teale, who is now at University of by Hopmann, unites twelve research Nottingham, holds a 20% position at groups with expertise in experimental the University of Oslo. He is the second and computational chemistry from nine researcher from the ABACUS ERC Nordic universities. Advanced Grant project of Trygve Helgaker to receive his own ERC pro- During the academic year 2017–2018, a ject, after Dr. Simen Kvaal in 2014. In number of prominent quantum chemists total, four members of the Hylleraas worked at the Academy of Science and Centre have received ERC grants in Letters in Oslo, on the project Molecules theoretical chemistry, the fourth in Extreme Environments, led by Trygve member being Hylleraas co-director Helgaker. Kenneth Ruud, who received a Starting Picture 3 Grant in 2011. Picture 2

Hylleraas annual report 2017 | 2018 11 z

2018 in Brief –

Picture 1: “Iron-Catalyzed Carbenoid-Transfer Reactions of Vinyl Sulfoxonium Picture 2: The exhibition Did you think? : An Experimental and Computational Study” by Vaitla, Bayer, at UiT, designed by Kathrin Hopmann and Hopmann was published in Angewandte Chemie in 2018.

Research Angewandte Chemie entitled Iron-Catalyzed Carbenoid Transfer Reactions of Vinyl Members of the Hylleraas Centre pub- Sulfoxonium Ylides: An Experimental and lished 62 papers in 2018. As in 2017, Computational Study. most of our papers were published in 2018 Picture 1 the area of chemical physics, the most popular journals being Journal of Chemi- cal Physics and Journal of Chemical Theory Outreach and dissemination in Brief and Computation. On March 8 2018, the exhibition Did you In the article NMR chemical shift analysis think? designed by Hylleraas PI Kathrin decodes olefin oligo- and polymerization Hopmann on women in science opened in Tromsø, as part of UiT’s 50-year an- activity of d0 group 4 complexes published in the prestigious Proceedings niversary. An extended exhibition was of the National Academy of Sciences of the later on display for two weeks in Ner- United States of America (PNAS) in June stranda Shopping Mall during the Re- 2018, Hylleraas PI Odile Eisenstein to- searcher Days (Forskningsdagene). The gether with co-workers from Zürich, exhibitions attracted much attention Osaka and UC Berkeley, established and two newspaper comments were chemical shifts as a predictive descrip- written, inspired by the exhibition. tor for catalytic activity of olefin polym- Picture 2 erization and oligomerization. In March 2018, the monograph Princi- In October 2018, Hylleraas PI Kathrin ples and Practices of Molecular Properties: Hopmann and Dr. Janakiram Vaitla Theory, Modelling and Simulations, written together with Assoc. Prof. Annette by Patrick Norman (Royal School of Bayer at UiT The Arctic University of Technology, Sweden), Hylleraas Dep- Norway published a combined exper- uty Director Kenneth Ruud and Trond imental and computational study in Saue (CNRS, Université Toulouse III-Paul

Hylleraas annual report 12 2017 | 2018 z

Picture 3: Cover of the monograph Picture 4: Cover of Journal of Chemical Theory and Computation Principles and Practices of Molecular September 2018 highlighting the work of Hylleraas members Properties, published in March 2018 Hima Bindu Kolli, Sigbjørn Løland Bore, and Michele Cascella on Wiley. on Hybrid Particle Field Molecular Dynamics

Sabatier, France), was published by area and spent one day at each institu- mole­cules with Trygve Helgaker as Wiley. The monograph provides a com- tion, interacting with students and staff. co-author. The article by Sen and prehensive yet accessible exploration Tellgren was later included in the 2018 of quantum chemical methods for the In July 2018, Kenneth Ruud was invited JCP Editors’ Choice Collection. determination of molecular properties to Wroclaw University of Science and of spectroscopic relevance. Technology as part of the city council The first Hylleraas Day was held at Picture 3 of Wroclaw’s visiting scientist program. Litteraturhuset in Oslo on November During his visit, he gave a broadly ori- 19 2018. Following an introduction by In May 2018, an interview with Hylleraas ented lecture on relativistic effects in the Hylleraas Communication Officer Director Trygve Helgaker, Theoretical chemistry and a specialized lecture on Elina Melteig, four PIs of the Hylleraas chemistry opens new possibilities — from multiphoton absorption. Centre gave short popular talks, cov- sciences to astrophysics, was pub- ering different aspects of the research lished on the University of Oslo web In September 2018, Hylleraas mem- at the centre. pages. In June 2018, the article New bers Dr. Hima Bindu Kolli, PhD student "designer " can make the in- Sigbjørn Løland Bore and Prof. Michele dustry save big amounts highlighting Cascella provided the cover Hybrid the research of Hylleraas members Particle Field Molecular Dynamics of the Dr. David Balcells, Dr. Ainara Nova, and September issue of Journal of Chemical Prof. Odile Eisenstein was published Theory and Computation. in Titan. Picture 4

During May 15–20 2018, Trygve Helgaker In October 2018, two articles published visited Massachusetts Institute of Tech- by Hylleraas members were selected nology (MIT), Boston University, and as feature articles of the Journal of Harvard University, by invitation of Chemical Physics: A local tensor that students as part of the Greater Boston unifies kinetic energy density and vorticity Area Theoretical Chemistry Lecture Series. in density functional theory by Dr. Sangita During his stay, he presented a lecture Sen and Dr. Erik Tellgren and Bethe–Sal- at MIT for theoreticians in the Boston peter correlation energies of and

Hylleraas annual report 2017 | 2018 13

2018 in Brief –

Picture 5: The closing of the 16th International Congress of in Menton, France, in June 2018 by the organizer Hylleraas PI Odile Eisenstein. The congress was co-sponsored by the Hylleraas Centre.

Conferences and meetings In June 2018, the 16th International External projects and funding Members of the Hylleraas Centre or- Congress of Quantum Chemistry (ICQC) was ganized several meetings during 2018. held in Menton, France, organized by In January 2018, dr. Abril Castro was In January, the meeting Adventures from Hylleraas PI Odile Eisenstein. More than awarded a Marie Sklodowska-Curie numerical quantum chemical methods to 500 theoretical chemists attended the Individual Fellowship for the project biological systems and beyond in honour highly successful congress — the larg- Relativistic and Dynamic effects in of Prof. Dage Sundholm (University of est conference in theoretical chemistry Computational NMR of Helsinki) was held at the Norwegian in 2018. transition-metal complexes, allowing her Academy of Science and Letters in Oslo, Picture 5 to spend two years at the Hylleraas with Hylleraas member Dr. Heike Fliegl Centre from 2019, under the super­ as chair of the organizing committee. In In the autumn of 2018, two mini-sympo- vision of Hylleraas PIs Michele Cas- March 2018, several Hylleraas members siums were held at the Hylleraas Centre. cella and Trygve Helgaker. attended Mathematical Methods in Quan- Profs. Kenneth Ruud and Bjørn-Olav tum Chemistry at the Mathematisches Brandsdal organized a mini-symposium In February 2018, Hylleraas PI Bjørn- Forschungsinstitut Oberwolfach in in September in connection with Nobel Olav Brandsdal was awarded a pres- Schwarzwald, Germany, with Helgak- laureate Prof. Arieh Warshel's promo- tigious Toppforsk Grant from the er as an organizer. The meeting Atoms, tion as Doctor Honoris Causa at UiT The Research Council of Norway. With a Molecules and Materials in Extreme En- Arctic University of Norway. In Novem- funding of about 30 MNOK, the project vironments was held at the Centre for ber, Frontiers in Density-Functional Theory Evolutionary Principles of Biocatalysts Advanced Study (CAS), the Norwegian was held in Oslo with two prominent from Extreme Environments will allow Academy of Science and Letters, in speakers in the field of density-func- him to establish a large-scale research June 2018, with Helgaker chairing the tional theory: Prof. Paola Gori-Giorgi program focusing on the mechanisms organizing committee. One month from Vrije Universiteit Amsterdam in the of cold adaptation in biological sys- later, Dr. André Laestadius organized the Netherlands and Asst. Prof. Emmanuel tems. Bransdal’s project was one of YoungCAS workshop Do Electron Current Fromager from Université de Strasbourg only eight FRINATEK Toppforsk appli- Densities Determine All There Is to Know? in France. cations funded in the 2017 Toppforsk in Asker outside Oslo. call.

Hylleraas annual report 14 2017 | 2018

Picture 6: Dr. André Laestadius was congratulated on the YRT grant by the Dean Morten Dæhlen and by Section Manager for Research Ingse Noremsaune at the Faculty of Mathematics and Natural Sciences in December 2018

In March 2018, the Hylleraas Centre was In July 2018, Hylleraas members Dr. awarded a grant from the Norwegian Simen Kvaal and PhD student Fabian Centre for International Cooperation in Faulstich were awarded a Peder Sather Education (SIU), Optical Probe Sensors grant together with Assoc. Prof. Lin Lin at Biological Environments, for develop- of UC Berkeley for the project A poste- ing joint curricula and research pro- riori error estimates for coupled-cluster gram with Tomsk State University and theory, investigating spatially adaptive St. Petersburg State University. The pro- coupled-cluster calculations using un- ject includes both the Oslo and Tromsø conventional local basis sets. branches of the Hylleraas Centre and in- volves on the Norwegian side Hylleraas In 2018, three members of the Hylleraas PIs Bjørn Olav Brandsdal, Luca Frediani, Centre were awarded FRINATEK grants Trygve Helgaker and Kenneth Ruud, from the Research Council of Norway. in addition to Hylleraas researchers Dr. André Laestadius won a prestig- Maarten Beerepoot and Heike Fliegl. ious Young Research Talent (YRT) grant Error estimates for coupled-cluster methods, In June 2018, the project Multi-resolution ground states and excited states — one methods including quantum chemistry, force of only eight such grants awarded in fields, and hybrid particle-field schemes by the call. Prof. Trygve Helgaker won a Hylleraas PI Michele Cascella ogether FRINATEK grant Magnetic chemistry, with Prof. Jürgen Gauss from the Uni- while Dr. Janakiram Vaitla was awarded versity of Mainz was approved by the a FRINATEK mobility grant for his pro- German Research Foundation as part ject Catalytic enantioselective sigmatropic of the Collaborative Research Centre / rearrangements of vinyl sulfonium ylides. Transregio TRR 146 Multiscale Simulation Picture 6 Methods for Soft-Matter Systems.

Hylleraas annual report 2017 | 2018 15 2018 in Brief –

Picture 7: Prof. Odile Eisenstein addressing the audience upon receiving the insignes d'officier dans l’ordre de la Légion d'honneur at the Institut de France in Paris

Personnel At the 58th Sanibel Symposium in Febru- Hylleraas PI Kathrin Hopmann was ary 2018, Dr. Andre Laestadius won the awarded the Gender Equality Prize of UiT On February 6 2018, Hylleraas PI Odile Talman Scholar Award for Mathematical The Arctic University of Norway on June Eisenstein was awarded the insignes Research in Quantum Chemistry, while 20 2018 for her efforts in promoting d'officier dans l’ordre de la Légion d'hon- PhD student Fabian Faulstich won the and in creating awareness about the neur at the Institut de France in Paris. IBM-Zerner Graduate Student Award. challenges facing women in academia The medal was presented by the Vice in general and in science, technology, President of the French Académie de In April 2018, Nobel laureate Prof. Arieh engineering, and mathematics (STEM) Sciences, Prof. Pierre Corvol. In 2013, Warshel from the University of South- in particular. In November, Hopmann Eisenstein was the first female chem- ern California, a collaborator of the was appointed associate editor of ist to be elected to the Académie de Tromsø-node of the Hylleraas Centre, Organometallics. Sciences. In June, she was elected pres- received an honorary doctorate from ident of the International Academy of UiT The Arctic University of Norway. Quantum Molecular Sciences (IAQMS). Prof. Jürgen Gauss from the Univer- At the same time, Hylleraas Director sity of Mainz (Germany), a frequent Trygve Helgaker was elected to the visitor to the Hylleraas Centre, was in Bureau of the Academy. Members of May 2018 elected foreign member of the Hylleraas Centre now hold two of the Norwegian Academy of Science the five positions in the Bureau of this and Letters. prestigious academy.

Picture 7

Hylleraas annual report 16 2017 | 2018 Egil. A. Hylleraas (1898–1965)

The Norwegian physicist Egil A. Hylleraas English translation: (1898–1965) helped usher in the era of sci- “In closing my presentation, I hope to have entific computing by carrying out accurate convinced the audience of the far-reaching calculations on helium, thereby confirm- opportunities that now exist for establishing a ing the validity of for theoretical chemistry, a quantum chemistry, more than one particle (1929), by predicting on the same footing as the physical quantum the stability of the anion, later theory.” detected in the Sun’s atmosphere (1930), and by performing the first calculation of “Importance of wave mechanics for under­ the cohesive energy of a molecular , standing the .” (1933) LiH (1930). In 1933, he introduced the term “kvantekjemi” into the Norwegian language:

“Idet jeg avslutter den utredning håper jeg at tilhørerne vil ha fått et inntrykk av at der nu foreligger ganske vidtrekkende muligheter for å bygge op en teoretisk kjemi, en kvante­ kjemi, på samme grunnlag som den fysikalske kvanteteori.”

Hylleraas annual report 2017 | 2018 17 Research Highlights –

Hylleraas annual report 18 2017 | 2018 The Hylleraas Centre carries out research on a broad range of topics in theoretical chemistry, with relevance not only to chemistry but also to physics, biology, and other related fields of science. Four such research topics are here highlighted, showcasing recent and ongoing work at the centre, including work in fundamental theoretical chemistry, the development of new computational methods and techniques, and the use of computational chemistry to address challenging questions in modern science, often in collaboration with experimentalists.

Hylleraas annual report 2017 | 2018 19 Research Highlights –

The Effect of Concentration on the Morphology of Charged Surfactant Assemblies in

Michele Cascella –

Cover page of JCTC highlighting the work.

Water/surfactant emulsions. You Sodium-dodecylsulphate (SDS) is one of The investigation of this phenomenon use it every day, but there’s much the most widely used ionic surfactants, by computer modelling faces two chal- more to learn from them. commonly found in daily-life products lenges. like toothpastes, shampoos, or kitchen – detergents. In scientific laboratories, 1) The irreducibly large systems that SDS is typically used for membrane need to be simulated, which must include solubilisation and extraction/mobili- a number of SDS molecules much larg- zation of integral membrane er than the number of SDS molecules into SDS micelles. contained in a typical micelle;

Despite the simplicity of the SDS mol- 2) the simulation times, which must be ecule, it has been reported that, above sufficiently long to allow SDS diffusion the critical micellar concentration, SDS and self-assembly. self-assembles in micelles of signifi- cantly different shapes. At low concen- The recent development of an approach trations, SDS forms regular spherical based on particle-mesh Ewald to treat constructs with a diameter roughly electrostatic interactions within the twice the length of one single mole- hybrid particle-field (hPF) method [2] cule. With increasing concentration, made it possible to study polyelectrolyte the spherical micelles metamorphose soft matter such as SDS using this ap- first into spheroidal aggregates, which proach. The hPF method has the advan- eventually evolve into microtubular tage of coupling a molecular-resolved structures of very long contour length resolution to a very fast calculation of [1]. molecular interactions, mediated by a density-based mesoscale potential [3].

Hylleraas annual report 20 2017 | 2018 Structure of SDS and the CG model Self assembled micelles observed used in hPF simulations. at different SDS concentrations.

After implementing the hPF elec- membranes or nucleic . The work trostatics in our software package was conducted at the Hylleraas Centre OCCAM, we investigated the self- by Dr. Hima Bindu Kolli, within her assembly process of SDS at different Marie-Sklodowska Curie Action concentrations [4]. Our results repro- (MSCA) project HYPERBIO, with some duced the qualitative trends observed important contributions from PhD in the experiment. Our simulations also student Sigbjørn L. Bore, under the confirmed the mechanism of forma- supervision of Prof. Michele Cascella. tion of the long microtubular micelles The study saw also the involvement of hypothesized by the experimentalists, external collaborators in China, Ger- consisting first in the formation of pro- many, and Japan. late ellipsoidal micelles, which then fuse along their long axis, merging References: the region of maximal curvature. 1 G. V. Jensen, R. Lund, J. Gummel, Finally, our study revealed that the T. Narayanan and J. S. Pedersen, transformation of the SDS micelles is Angew. Chem., Int. Ed. 2014, 53, 11524−11528. non-trivially dependent on the effective 2 Y.-L Zhu, Z.-Y. Lu, G. Milano, G. dielectric constant of the medium [4]. A.-C. Shi and Z.-Y. Sun, Phys. Chem. Chem. Phys. 2016, 18, 9799−9808. The ability to describe the behaviour 3 G. Milano and T. Kawakatsu, of soft polyelectrolyte matter has laid J. Chem. Phys. 2009, 130, 214106. a foundation for the future 4 H. B. Kolli, A. De Nicola, S. L. Bore, K. development of the hPF method Schäfer, G. Diezemann, J. Gauss, T. towards complex biological assemblies Kawakatsu, Z.-Y. Lu, Y.-L. Zhu, G. of polyanionic nature, like bacterial Milano and M. Cascella, J. Chem. Theory Comput. 2018, 14, 4928-4837.

Hylleraas annual report 2017 | 2018 21 Research Highlights –

Opening the Catalysis Black-Box with Microkinetic Models Including Off-Cycle Species

Ainara Nova and David Balcells –

Calculations were combined In the field of homogeneous catalysis, In a series of DFT studies [1], we have with experiments in the study density functional theory (DFT) is a developed a stereoelectronic model for of Suzuki-Miyaura catalysts to key tool in the rational design of new the optimization of palladium catalysts catalysts. When combined with elec- used in the Suzuki-Miyaura cross- determine the key steps of the tronic structure analysis tools, DFT coupling reaction – a key synthetic tool mechanism, both inside and calculations yield stereoelectronic in the production of pharmaceuticals outside the catalytic cycle. The models that can be used to guide and functional materials. In collabo- results were combined with mi- experiments in the development of ration with the experimental group cro-kinetic models, enabling the more active, robust and selective cata- of Prof. Hazari (Yale Univ., USA), the development of new catalysts lysts. The most common approach is to studies showed that the allyl with higher activity. compute the catalytic cycle – the loop supporting the metal center can be used – of elementary steps connecting reac- to control the off-cycle chemistry of the tants to products while recovering the system. The key off-cycle steps were 1) catalyst. Once the cycle is known, the the activation of the pre-catalyst, which critical step is identified and en­hanced was promoted to increase activity, and by modifying the system in a rational 2) the formation of dimers, which was manner. Despite its success in several excluded due to their poor reactivity. systems, this approach can fail when In line with the experiments, the the mechanism involves complex calculations showed that catalytic reaction networks. These may include activity is maximized by embedding the off-cycle species lying outside the allyl group within the indenyl moiety main catalytic cycle. Off-cycle species and by adding a tert-butyl group at the can be connected to in-cycle interme- 1-position (Figure 1). The indenyl accel- diates, undermining the overall effi- erated pre-catalyst activation through ciency of the catalytic system. a H-shift mechanism, whereas the

Hylleraas annual report 22 2017 | 2018 Cross-coupling catalyst design based on the optimization of both the in- and off- cycle steps.

tert-butyl substituent introduced the used to determine the key steps. Time References: steric bulk required to prevent - evolution simulations revealed the key 1 (a) D. P. Hruszkewycz, D. Balcells, ization. A similar approach was used to interplay between the C–N cleavage L. M. Guard, N. Hazari and M. Tilset, evaluate the impact of nickel(I) species step and the formation of the adduct. J. Am. Chem. Soc., 2014, 136, 7300–7316; (b) D. P. Hruszkewycz, in the Ni-catalyzed cross-coupling of In this framework, catalytic activity L. M. Guard, D. Balcells, N. Feldman, aryl sulfamates [2]. could only be maximized by optimizing N. Hazari and M. Tilset, Organome- both parameters. tallics, 2015, 34, 381–394; (c) P. R. In catalytic systems following compli- Melvin, A. Nova, D. Balcells, W. Dai, Figure above cated mechanisms, the inclusion of the N. Hazari, D. P. Hruszkewycz, H. P. Shah and M. T. Tudge, ACS Catal., off-cycle chemistry adds further com- In summary, we combined theory with 2015, 5, 3680–3688; (d) P. R. Melvin, plexity. This scenario was illustrated experiments to build rational models D. Balcells, N. Hazari and A. Nova, by the iron-catalyzed hydrogenolysis of for catalyst design. With a rich rep- ACS Catal., 2015, 5, 5596–5606. amides [3]. The mechanism involved the resentation of the underlying mecha- 2 M. M. Beromi, A. Nova, D. Balcells, following steps: 1) hydrogenation of the A. M. Brasacchio, G. W. Brudvig, nisms, catalytic activity was enhanced amide to hemiaminal (metal-catalyzed), L. M. Guard, N. Hazari and by maximizing the productive reactions 2) C–N by intramolecular D. J. Vinyard, J. Am. Chem. Soc., occurring inside the catalytic cycle, 2017, 139, 922–936. proton transfer (amide co-catalyzed, while minimizing the detrimental ones 3 L. A. Artús-Suárez, Z. Culakova, yielding amine and formaldehyde) and occurring outside [4]. D. Balcells, W. H. Bernskoetter, 3) hydrogenation of formaldehyde to O. Eisenstein, K. I. Goldberg, methanol (metal-catalyzed). In addi- N. Hazari, M. Tilset and A. Nova, tion, the amide reactant could block the ACS Catal., 2018, 8, 8751–8762. catalyst by forming stable unreactive 4 D. Balcells and A. Nova, ACS Catal., adducts. Due to the complexity of the 2018, 8, 3499–3515. mechanism, a micro­kinetic model was

Hylleraas annual report 2017 | 2018 23 Research Highlights –

A Benign, Inexpensive & Air-Stable Catalyst for Making Important Chemicals

Kathrin H. Hopmann –

Figure 1: Dr. J. Vaitla, Assoc. Profs. A. Bayer and K. H. Hopmann are involved in the reported work.

The Hylleraas Centre is applying A novel reaction based on iron Vaitla, Bayer and Hopmann is based on computational methods to under- The Hylleraas PI Assoc. Prof. Kathrin an inexpensive, and environmentally stand and design novel chemical H. Hopmann has together with her benign metal, iron (Figure 2), as part of the air-stable FeBr catalyst. reactions. Particular focus is on co-workers Assoc. Prof. Annette Bayer 2 reactions based on sustainable and Dr. Janakiram Vaitla (Figure 1) The mechanism such as iron, which is in- published a combined experimental and computational study in Angewandte The mechanism of the new reaction expensive and environmentally Chemie entitled Iron-Catalyzed Carbenoid was a significant puzzle to solve, in benign. We report a novel pro- Transfer Reactions of Vinyl Sulfoxonium particular, because a byproduct was tocol employing the air-stable Ylides: An Experimental and Computational isolated (shown in orange in Figure catalyst FeBr2 for making inter- Study [1]. The study presents a method 3). It was unclear if the byproduct is mediates of high chemical value. for the synthesis of valuable chemical part of the catalytic reaction. There- – intermediates such as indolizines, fore, a series of control experiments pyrroles, 3-pyrrolin-2-ones, and furans. and a detailed computational analysis For example, indolizines display im- were performed. The computational portant biological activities, including work revealed that the experimen- antitumor, anti-inflammatory, and anti­ tally observed byproduct is in fact viral effects. The method reported by an off-cycle species, which is formed

Hylleraas annual report 24 2017 | 2018 Figure 2: Iron – an inexpensive and environmentally benign metal. (Colourbox/Olekcii Mach).

fast, but also is rapidly converted back to a carbene, which can move forward to give the desired indolizine product. The theoretical work also showed very similar energy barriers for forming different types of chemical products, furans or indolizines, shown in green and black respectively, in Figure 3. The preferred product is dependent on the substituents on the substrate and on the nature of the metal catalyst. The non-precious metal iron gives indolizines, whereas the precious metal iridium gives furans.

References: Figure 3: Computed energy profile for forming 1 J. Vaitla, A. Bayer, K. H. Hopmann indolizines using an inexpensive iron catalyst Angewandte Chemie 2018, 57, (from [1]). 16180-16184

Hylleraas annual report 2017 | 2018 25 Research Highlights –

Simulation of Relativistic Effects in Materials from First Principles

Marius Kadek and Michal Repisky –

Symmetry and mathematics have relativity (“relativistic effects”) that the topological insulators good candi- enabled a leap in the modelling cannot be neglected in materials dates for components of a quantum of relativistic effects in solid-state containing heavier elements. To incor- computer and their theoretical and porate special relativity into quantum experimental study is the subject of materials, paving the way for quan- mechanics, the Schrödinger equation intensive research in the solid-state titative studies of novel materials must be replaced with its relativistic physics community. with potential applications in counterpart, the Dirac equation. quantum computers. Nowadays, a major challenge in com- – In relativistic quantum mechanics, putational solid-state physics is the the orbital angular momentum of an capability of first-principle models to electron is coupled to its spin. This treat relativistic effects non-perturba- The properties and electronic struc- spin-orbit coupling in materials is tively when modelling material prop- ture of atoms, molecules, and responsible for the emergence of erties driven by atomic-core regions are determined by the fundamental remarkable states of matter that are and/or spin-orbit interaction. Devel- laws of quantum mechanics. Simula- protected by the time-reversal symme- opment of methods that account for tion and theoretical prediction of these try. Materials in such a state are bulk in- relativistic effects in atoms and mole- properties require solving complicated sulators, but conduct electricity on their cules has been the focus of our group equations, such as the Schrödinger surface. Such materials are called top- in the Hylleraas Centre and results of equation. Another fundamental theory ological insulators, and the symmetry- this work are available through the of the 20th century – Einstein’s special protection of their surface states makes ReSpect (Relativistic Spectroscopy) theory of relativity – accounts for the topological insulators resistant to program package on the website www. fact that the speed of light is finite, non-magnetic impurities present in respectprogram.org. Extending these leading to the effects of special realistic samples. This resistance makes relativistic methods to computer

Hylleraas annual report 26 2017 | 2018 The honeycomb structure of two-dimensional and germanene (left) – heavier analogues of . The band of germanene touches the conduction band (right) at a pair of Dirac points. The spin-orbit copuling opens a small band gap between these bands, classifying germanene as a two-dimensional topological insulator exhibiting the quantum spin Hall effect.

simulations of solids was the goal of Despite the fact that solving the all- the PhD thesis of Marius Kadek that electron Dirac equation for large was defended in August 2018. The PhD samples of materials poses numerous work offers a comprehensive theoret- challenges to the employed computa- ical foundation and an efficient com- tional approaches, we believe that our puter implementation of a method that work significantly pushes boundaries solves the four-component all-electron of relativistic calculations of solids, that Dirac-Kohn-Sham equation in local up to now have been hindered by var- Gaussian-type bases. The method uses ious uncontrolled approximations. time-reversal symmetry and the These approximations prevented mathematically beautiful formalism of studying magnetic properties of mate- complex-quaternion algebra to signif- rials, topological phases, and other icantly reduce the methodological and material properties for which the computational complexity of the inclusion of relativity is essential. approach. In addition, the work proves Further research along this line will be its potential to shift the paradigm conducted at the Hylleraas Centre. in computational solid-state physics by demonstrating that results well-converged with respect to the one-electron basis can be obtained with local bases developed for molecules.

Hylleraas annual report 2017 | 2018 27 ResearchCareer Highlights Development – –

Career Development

A Hylleraas Career Development they drafted the Hylleraas Career and senior scientists. An 11-page KUPP Programme has been set up to Development Programme (HCDP), report written by Olaug Kristine Brin- improve the support for the many whose central elements are illustrated gager and Trygve Helgaker was dis- in Fig.1. It provides the foundation for tributed to all participants and others young reseachers at the centre. career development at the centre. at the University of Oslo, including the – University leadership, who enthusias- In the autumn of 2018, the Hylleraas tically supported the initiative. During Career development and improved sup- Centre contacted Senior Advisor Olaug 2019, all participating CoEs will revise port for early-stage researchers is an Kristine Bringager in the Research Sup- and improve their career development integral part of the Hylleraas Centre as port Office at the University of Oslo for and support based on the ideas and stated in our proposal: “To prepare the advice on career development. After guidelines developed in KUPP. A third young researchers for careers as scien- some discussions, a broader initiative KUPP meeting is planned towards the tific or industrial leaders, a mentorship for career development, involving all end of 2019, to share ideas and expe- programme will be set up and detailed Centres of Excellence (CoEs) at the Uni- riences in our effort for a better career in a Career Development Plan. We will versity of Oslo, was launched. In the development and support of young re- encourage participation in courses that Career Development Pilot Programme searchers, and for building a consistent provide transferable skills relevant to (KUPP), senior members of all Centres framework for support throughout the academia and industry such as ethics, of Excellence at UiO were invited to whole campus. communication, scientific writing, - take part in two meetings, each of one ership, business creation, and entrepre- full day’s duration, in October and During 2019, the Hylleraas Centre is neurship, as offered by the Research November 2018. Here experiences committed to develop further its orig- Leadership Programme at UiO and the would be shared and ideas for improve- inal initiatives for career development, High North Academy at UiT.” ments would be developed. and to begin the operative phase with the implementation of the first policies. The need for career development and The KUPP meetings, which were devel- support was emphasized by Prof. oped and led by Bringager in partner- Michele Cascella and Assoc. Prof. ship with the Hylleraas Centre, were Kathrin Hopmann early in the appli- highly successful, with participation cation process. In the spring of 2018, from eight CoEs including directors

Hylleraas annual report 28 2017 | 2018 Hylleraas Director Trygve Helgaker opening the first KUPP meeting Hylleraas PIs Michele Cascella and at Lysebu Conference Centre in Oslo on October 30, 2018. Kathrin Hopmann, who initiated the work on career development at the Hylleraas Centre.

Mentor Career Conferences Transferable skills Development Plan courses

Chosen within Written with mentor Participation + presen- Courses in entrepreneurship/ 6 months from (shared with PhD tation at international scientific writing/research mentor pool supervisor). Updated conference (not leadership every 12 months organized by Hylleraas)

PhD Mandatory Mandatory Mandatory (1-2) Mandatory (1)

Postdoc Mandatory Mandatory Mandatory (1-2) Strongly encouraged

Researcher Voluntary Mandatory Strongly encouraged Voluntary

Brief overview of tentative Hylleraas Career Development Programme (HCDP)

Hylleraas annual report 2017 | 2018 29 Almlöf–Gropen Lecture –

Hylleraas annual report 30 2017 | 2018 The Almlöf–Gropen Lecture Series

The Almlöf–Gropen Lecture Series was established by the CTCC in 2008 to honour the memory of two pioneers of quantum chemis- try in Norway: Prof. Jan Almlöf (1945–1996) at the University of Oslo and Prof. Odd Gropen (1941–2005) at UiT The Arctic University. Each year, a prominent theoretical chemist is invited to deliver the Almlöf- Gropen lecture at the Hylleraas Centre in Oslo and Tromsø, targeting a broad audience.

Previous Almlöf–Gropen lecturers _

2008 Prof. Bjørn Roos 2013 Prof. Henry F. Schaefer University of Lund, Sweden: University of Georgia, Athens, USA: Multiconfigurational quantum chemical From donor-acceptor complexes to methods and heavy element chemistry nitride nanorods

2009 Prof. Tom Ziegler 2014 Prof. Leo Radom University of Calgary, Canada: University of Sydney, Australia: Analyzing complex electronic structure Adventures in free chemistry: calculations on large molecules in simple a computational approach chemical terms

2010 Prof. Michele Parrinello 2015 Prof. Arieh Warshel ETH Zürich, Switzerland: University of Southern California, USA: Through mountains and valleys How to model the action of complex with metadynamics biological systems on a molecular level

2011 Prof. Pekka Pyykkö 2016 Prof. Emily Carter University of Helsinki, Finland: Princeton University, USA: Relativity and chemistry: Quantum solutions for some recent results a sustainable energy future

2012 Prof. Harry B. Gray Caltech, USA: The 21st century solar army

Hylleraas annual report 2017 | 2018 31 Almlöf–Gropen Lecture –

Prof. Jack Simons delivering the Almlöf–Gropen lecture 2017 at the Department of Chemistry, University of Oslo

Almlöf–Gropen Lecturer 2017: Professor Jack Simons

The Wonderful World Professor Jack Simons, University of Medal of the International Academy of of Molecular Anions Utah, was the first Almlöf–Gropen Lec- Quantum Molecular Sciences (1983) turer at the Hylleraas Centre, presenting and the Joseph O. Hirschfelder Prize in – his talk The Wonderful World of Molecular Theoretical Chemistry (2013). October 4, 2017, Clarion Hotel Anions in the first week of operations of The Edge, Tromsø the Hylleraas Centre. His first lecture In his lectures, Simons discussed what was given at the final CTCC meeting in happens to a molecule when an electron and October 5, 2017, UiO Tromsø, thereby nicely bridging the two attaches to it and enters and anti-bond- Centres of Excellence. Jack Simons is ing or binding orbital. In a pedagogical Henry Eyring Scientist and Professor manner, he introduced the audience to Emeritus of Chemistry at the University the rich and surprising chemistry of of Utah. He graduated from the Uni- molecular anions and the many meth- versity of Wisconsin (Madison) with odological challenges these systems a PhD in Chemistry in 1970 and has present to quantum chemists. since published 335 articles and four textbooks. Jack Simons is the recipi- ent of numerous awards including the

Hylleraas annual report 32 2017 | 2018 Prof. Walter Thiel delivered the Almlöf–Gropen lecture 2018 at the Department of Chemistry, University of Oslo

Almlöf–Gropen Lecturer 2018: Professor Walter Thiel

Chemistry with the Computer In his lecture, Walter Thiel discussed – the current status and prospects of quantum chemistry, explaining how May 14 (UiO) and advances in methodology and hardware May 15 (UiT) 2018 have led to situation where accurate methods can be applied to complex Walter Thiel is the Director of Max- systems so that challenging chemical Planck-Institut für Kohlenforschung problems can nowadays often be solved and Honoary Professor of Universität by the interplay of experiment and Düsseldorf. He received both his B.Sc. theory. Specifically, he discussed high- (1971) and Ph.D. (1973) in chemistry ly accurate ab initio calculations on from Universität Marburg. He is the the spectroscopy of small molecules, author of 589 publications and the density functional studies of transition recipient of numerous awards and metal catalyzed reactions, semiempirical honours, including the Schrödinger excited-state dynamics simulations, Medal (2002), the Liebig Medal (2012) and QM/MM modelling of complex and the Kolos Medal (2017). .

Hylleraas annual report 2017 | 2018 33 Meetings and Events –

Hylleraas annual report 34 2017 | 2018 CTCC Final Meeting – Hylleraas First Meeting

Clarion Hotel The Edge, Tromsø, October 2–4 2017

The 10th and last CTCC meeting was held by the principal investigators at the a presentation of its history and a at Clarion Hotel The Edge in Tromsø centre. Particular attention was given visit to its micro-brewery, which now October 2–4 2017. Celebrating the suc- to how CTCC had influenced their occupies its premises. cess of the CTCC 2007–2017, all current research activities. In addition, five and previous members of the centre previous CTCC members gave talks, Since this meeting also marked the were invited to this event. The scientific focussing on the role CTCC had played start of a new centre, the Hylleraas Cen- program consisted of 20 talks. Following in their careers. tre for Quantum Molecular Sciences, an overview of the research at the CTCC its Director Prof. Trygve Helgaker gave given by its Director Trygve Helgaker, The social program included a guided an overview of the planned research more detailed presentations were given tour at the local brewery Mack with activities for the Hylleraas Centre.

Participants at the CTCC Final Meeting – Hylleraas First Meeting at Clarion Hotel The Edge in Tromsø, October 2017.

Hylleraas annual report 2017 | 2018 35 Meetings and Events –

Molecules in Extreme Environments

Trygve Helgaker – Centre for Advanced Study 2017–2018

During the academic year 2017– of Education and Research. Every year, molecules in strong magnetic fields, 2018, a number of prominent three groups work at CAS, having been ionization in a magnetic field, molec- quantum chemists worked at the selected during an application process ular excitations and spectra in strong two years earlier. The project Molecules magnetic fields, closed-shell paramag- Academy of Science at Letters in in Extreme Environments was led by Hyl- netism, density-functional theory in Oslo, participating in the project leraas Director Trygve Helgaker during magnetic fields, confined electronic Molecules in Extreme Environ­ the academic year 2017–2018. systems, melting in strong magnetic ments, led by Hylleraas Director fields, magnetically induced currents, Trygve Helgaker. In addition to the group leader, the CAS and quantum electrodynamics. The CAS – group consisted of twelve fellows, all project was characterized by openness quantum chemists with complementary and willingness to learn from one an- expertise in electronic-structure theo- other in direct collaboration or during The Centre for Advanced Study (CAS) at ry (see Figure). In addition, Hylleraas the many informal seminars, which the Norwegian Academy of Science and members Dr. Alex Borgoo and Dr. Erik often lasted two or even three hours. Letters is an independent foundation Tellgren were frequent visitors to CAS Collaborations initiated during the CAS that furthers fundamental, curiosity- taking part in several of the projects. project are still ongoing. In a final one- driven research in the fields of humani- week gathering of all CAS participants ties, social sciences and natural scienc- The research at CAS, concerned a vari- in November 2019, these projects will es, funded by the Norwegian Ministry ety of themes such as the stability of be finalized.

Hylleraas annual report 36 2017 | 2018 Meetings and Events –

Stella Stopkowicz giving a CAS Members of CAS attended the 2018 Abel Prize award ceremony for Robert Langlands seminar on October 27 2017. in the University Aula in Oslo on May 22 2018.

CAS Fellows

PhD student Prof. Prof. Senior Lecturer Dr. Prof. Maria Dimitrova Jürgen Gauss Wim Klopper Elke Pahl Lukas Pasteka Trond Saue University of Helsinki, University of Mainz, Karlsruhe Institute of Massey University, Comenius University, University of Toulouse, Finland Germany Technology, Ger- Auckland, New Slovakia France many Zealand

Prof. Dr. Dr. Prof. Asst. Prof. Prof. Peter Schwerdtfeger Krista Steenbergen Stella Stopkowicz Dage Sundholm Andy Teale Hans Joachim Werner Massey University, Massey University, University of Mainz, University of Helsinki, University University of Stuttgart, Auckland, New Auckland, New Germany Finland of Nottingham, UK Germany Zealand Zealand

The members of the CAS organized in fellows interacted with members of the 2018 two three-day conferences spon- Hylleraas Centre and regularly attended sored by the Hylleraas Centre: Adven- the Hylleraas Friday seminars, where tures from numerical quantum chemical many also give presentations. methods to biological systems and beyond (January 15–17) and Atoms, molecules and materials in extreme environments (June 4–6). During the CAS year, many CAS

Hylleraas annual report 2017 | 2018 37 Meetings and Events –

Participants of the 2018 Dalton Workshop at the Hylleraas Centre

2018 Dalton Workshop

Hylleraas Centre, University of Oslo, January 10–12 2018

Members of the Hylleraas Centre The 2018 Dalton meeting was held at flexibility for further development and are active developers of the Dal- the Hylleraas Centre in Oslo January 10 extensions. ton program system, a decades- to 12, 2018. The meeting was organized by Hylleraas Software Engineer Simen In the Dalton community we have old collaborative effort of Scan- Reine and was attended by 19 Dalton therefore over the last decade seen that, dinavian quantum chemists. In developers. The Dalton program suite although many of the groups still use 2018, the annual Dalton workshop provides extensive functionality for the Dalton for their core activities, they was organized by the Hylleraas calculations of molecular properties, have at the same time developed new Centre. and is, together with MOLCAS, impor- codes to meet their own scientific goals. – tant for the strong position of quan- The most important decision of the Dal- tum chemistry in the Scandinavian ton 2018 meeting was to develop a joint countries. The main challenge with platform for these codes, with the aim such established codes is to keep the of establishing a flexible environment important parts of the code updated for developers and users, and of keeping and modernized to meet new require- the strong community connected, active ments and competition, while retaining and vital.

Hylleraas annual report 38 2017 | 2018 Participants of the conference Adventures from numerical quantum chemical methods to biological systems and beyond at the Norwegian Academy of Science and Letters in January 2018.

Adventures from Numerical Quantum Chemical Methods to Biological Systems and Beyond

The Norwegian Academy of Science and Letters, Oslo, January 15–17 2018

A conference in honour of Prof. From January 15 to 17 2018, the meet- meeting was hosted by CAS with sup- Dage Sundholm on the occasion ing Adventures from numerical quantum port from the Hylleraas Centre. Apart of his 60th birthday gathered chemical methods to biological systems from Hylleraas members Dr. Heike and beyond was held in honour of Prof. Fliegl (chair) and Prof. Trygve Helg- 70 participants for three days of Dage Sundholm (University of Helsinki) aker, the organizing committee con- science and celebration at the at the Norwegian Academy of Science sisted of Dr. Mikael Johansson (Uni- Norwegian Academy of Science and Letters in Oslo. The meeting, which versity of Helsinki), Dr. Raphael Berger and Letters in January 2018. gathered about 70 participants, was (University of Salzburg), Dr. Michael – organized as a surprise for Sundholm, Patzschke (Helmholtz-Zentrum Dres- who spent much of the academic year den–Rossendorf), and Prof. Ville Kaila 2017–2018 at the Centre for Advanced (Technical University Munich). During Study (CAS) at the Norwegian Academy the meeting, a total of 34 oral and of Science and Letters, on the project 17 poster presentations were given. Molecules in Extreme Environments. The

Hylleraas annual report 2017 | 2018 39 Meetings and Events –

Participants of the workshop Top right: Organizers of the workshop (from left): Eric Cancés, Lin Lin, Trygve Helgaker, (Archives of the Mathematisches and Gero Friesecke (Archives of the Mathematisches Forschungsinstitut Oberwolfach) Forschungsinstitut Oberwolfach) Down right: Mathematisches Forschungsinstitut Oberwolfach

Mathematical Methods in Quantum Chemistry

Mathematisches Forschungsinstitut Oberwolfach, Germany March 18–24 2018

The workshop Mathematical University of California, Berkeley) was discussions. Several members of the Methods in Quantum Chemistry held at the Mathematisches Forschungs- Hylleraas Centre presented their work: held at the Mathematisches institut Oberwolfach (MFO) in Schwar- Ph.D. student Fabian Faulstich, Dr. Si- zwald, Germany. The aim of the work- men Kvaal, Dr. Andre Laestadius, Prof. Forschungsinstitut Oberwolfach shop was to be a meeting place for Thomas Bondo Pedersen, Ast. Prof. (MFO) in March 2018 brought quantum chemists and mathematicians Andy Teale, and Dr. Erik Tellgren. In together quantum chemists and to report and discuss recent advances addition, presentations were made by mathematicians working in the on topics such as coupled-cluster theory, Prof. Jürgen Gauss and Prof. Trond area of electronic structure theory direct approximation schemes in full Saue, fellows of the project Molecules to report and discuss recent configuration-interaction (FCI) theory, in Extreme Environments at the Centre advances in the field. interacting Green’s functions, foun- for Advanced Study in Oslo. – dations and computational aspects of density-functional theory (DFT), low- The MFO is situated in the beautiful rank tensor methods, quantum chem- surroundings of Schwarzwald, pro- istry in the presence of a strong mag- viding a wonderful setting for the From March 18 to 24, the workshop Math- netic field, and multiscale coupling of workshop. Each year, MFO holds 48 ematical Methods in Quantum Chemistry quantum simulations. one-week workshops in mathematics organised by Eric Cancès (École des and related fields. Ponts ParisTech, Paris), Gero Friesecke The MFO workshop was attended by (Fakultät für Mathematik, TU München), 45 participants and the programme Trygve Helgaker (Hylleraas Centre) and consisted of informal presentations Lin Lin (Department of Mathematics, of ongoing projects followed by lively

Hylleraas annual report 40 2017 | 2018 Meetings and Events –

Participants of the conference Atoms, Molecules Toru Shiozaki, Stella Stopkowicz and Materials in Extreme Environments and Jürgen Gauss relaxing on the balcony during the conference

Atoms, Molecules, and Materials in Extreme Environments

The Norwegian Academy of Science and Letters, Oslo, June 4–6 2018

The conference Atoms, Mole­ To mark the end of the successful project ing of neon under high pressure and cules, and Materials in Extreme Molecules in Extreme Environments held modelling of hydrogen-rich planetary Environments held at the Nor- at the Centre for Advanced Study materials. The meeting was organized (CAS) during the academic year by CAS fellows Prof. Trygve Helgaker wegian Academy of Science and 2017–2018, a small conference Atoms, (Director of the Hylleraas Centre), Prof. Letters in early June 2018 marked Molecules, and Materials in Extreme Trond Saue (Université Paul Sabatier, the end of the project Molecules Environments was held at the Norwegian Toulouse, France) and Prof. Peter in Extreme Environments at the Academy of Science and Letters June Schwerdtfeger (Massey University, Centre for Advanced Study (CAS) 4–6 2018, gathering about fifty top ex- Auckland, New Zealand). The meeting in the academic year 2017–2018. perts in the field to present and dis- was supported by the Hylleraas Centre – cuss their work. During the meeting, and attended by many of its members. twenty-four talks and thirteen posters were presented, covering topics such as molecules on stars and neutron stars, synthesis of new compounds under high pressure, melt-

Hylleraas annual report 2017 | 2018 41 Meetings and Events –

Opening of congress by representative Odile Eisenstein serving Mike Robb at of Menton at Le Palais d’Europe the banquet dinner at Le Palais d’Europe

16th International Congress of Quantum Chemistry (ICQC)

Le Palais d'Europe, Menton, France, June 18–23 2018

With more than 500 participants, China, and the 2012 edition in Boul- from the University of Montpellier, of the 16th International Congress of der, Colorado, USA. The 2018 congress which Odile Eisenstein is a member. Quantum Chemistry held in Men- was held in “Le Palais de l’Europe”, in Menton, France, June 18–23 2018. More than 500 participants from 43 ton, France was the largest con- It brought together the international countries and all continents attended ference in theoretical chemistry community of theoretical chemists for the meeting, the European contingent in 2018. The highly successful a one-week conference aimed at pre- being the largest. An effort was made congress was organized by Hyl- senting the state of the art and latest to attract young participants who do leraas PI Prof. Odile Eisenstein. advances in terms of developments not yet have a PhD via an attractive – and applications in the field of theo- registration fee. As a result, one third retical and computational chemistry. of the participants were students. The scientific content of the meeting The 16th ICQC has been held every three was established in collaboration with A single-session format allowed the years under the auspices of the Inter- the scientific board of ICQC, formed by audience to follow the entire program. national Academy of Quantum Molec- members of the IAQMS. The local organ- All talks were by invitation only and all ular Science (IAQMS) since 1973. The izing committee consisted of a group other contributions were presented as 2015 ICQC was organized in Beijing, of academics, researchers and students posters. The 49 speakers, among them

Hylleraas annual report 42 2017 | 2018 Meetings and Events –

City of Menton viewed from the West

14 female, came from 23 countries. In specialize in theoretical chemistry, illus- • Strong Correlation in Electronic addition of 45 scientific lectures, four trates the increasing impact of theory Structure Theory, Emmanuel presentations honoured the founders and computation among chemists. Fromager, Chantal Daniel, and of the IAQMS: Per-Olof Löwdin, Rob- Trygve Helgaker, Strasbourg ert Parr, John Pople, Raymond Daudel, As is the tradition, several satellite (France) Alberte and Bernard Pulmann. These meetings were organized before and • Photoinduced Processes in lectures were much appreciated and after the main event, each attracting Embedded Systems, Claudia Fillipi, the daughter and son of Pople, who between 90 and 150 participants: Filippo Lipparini, and Benedetta attended the lecture about their father, Mennucci, Pisa (Italy) were warmly applauded. • Theoretical Studies of Magnetic • Understanding Chemistry and Systems: Methodological Develop- Biochemistry with Conceptual More than 300 posters were presented ments and Applications, Nathalie Models, Stéphane Humbel, in two sessions. A total of 22 poster Guihery and Jean-Paul Malrieu, Lynn Kamerlin, and Sason Shaik, prizes, offered by Wiley, the Royal Toulouse (France) Marseille (France) Society of Chemistry and the American • Computational Catalysis for The topics of these satellites were Institute of Physics, were awarded to Sustainable Chemistry, Feliu approved by the chair and the scien- presenters following a selection by a Maseras and Keiji Morokuma, tific board of ICQC but were organised committee headed by Prof. Mike Robb. Tarragona (Spain) independently of the main meeting. • Computational Chemistry Meets The meeting received strong financial Artificial Intelligence, Ursula support from the city of Menton and Röthlisberger, Lausanne a number of scientific and academic (Switzerland) groups, publishers and software developers. This wide support, includ- ing support from journals that do not

Hylleraas annual report 2017 | 2018 43 Meetings and Events –

Do Electron Current Densities Determine All There Is to Know?

Andre Laestadius – YoungCAS Workshop, Centre for Advanced Study Holmen Fjordhotell, Asker, July 9–13 2018

During July 2018, Dr. Andre Laestadius organized a workshop on the This fact has caused serious complica- Hohenberg-Kohn theorem financed by the Centre for Advanced Study tions when attempting to generalize the (CAS). The week-long workshop was entitled Do Electron Current Hohenberg-Kohn theorem to the total current density regime. Densities Determine All There Is to Know? and the invited researchers included chemists, physicists and mathematicians. Members of the The workshop addressed this partic­ Hylleraas Centre who participated at the YoungCAS workshop were ular problem of Hohenberg-Kohn-like researchers Alex Borgoo, Simen Kvaal, Andy Teale, and Erik Tellgren, theorems in a density-functional and postdoctoral fellow Sangita Sen. setting that also includes magnetic – fields – current-density-functional theory. The aim was to construct The focus of the workshop was generali- molecules are based. However, when a a mathematically rigorous foun- zations of the Hohenberg-Kohn theorem system also includes a magnetic field, dation for magnetic field effects in in density-functional theory. The the quantum-mechanical description density-functional theory. Further ­ original result states that the ground- includes a vector potential. Therefore more, there was also a focus on state particle density determines the other densities than the particle density whether such a formulation can pave electric potential of the system from become relevant when describing the the way for new kinds of practical which the density originates. It was system: the paramagnetic, the total and approximations. It is a long-standing proved in 1964 by Pierre Hohenberg the diamagnetic current densities. The and still open problem whether, in the and Walter Kohn. It is commonly total current density is the sum of the language of density-functional theory, regarded as the fundament on which paramagnetic and diamagnetic current the particle and the total current densi- density-functional computations for density. The diamagnetic current density ties determine all properties of the cor- the electronic structure of atoms and explicitly depends on the vector potential. responding system. Here system refers

Hylleraas annual report 44 2017 | 2018 Hylleraas member Dr. André Laestadius organized the YoungCAS workshop Do electron current densities determine all there is to know? in July 2018.

to a fixed number of quantum particles importantly, it pinpoints the failure that are described by the Schrödinger why this route cannot be followed in equation or some version of it, e.g., the current-density-functional theory using Maxwell-Schrödinger model. Previous either the paramagnetic current density attempts have been shown to be in or the total density. HK1 states that if two error or suffer from inconsistencies. systems share a ground-state density However, while using a different model then they also share a ground state. than the Schrödinger equation, the HK2 strengthens this fact to a statement Maxwell-Schrödinger model, Erik Tellgren of shared potentials if the considered and Michael Ruggenthaler, independently, Hamiltonians have the unique-contin- have shed new light on the existence uation property from sets of positive of a Hohenberg-Kohn-result in density- measure. This property guarantees functional theory with magnetic fields. that, if a solution of the Schrödinger equation vanishes on a set of positive The main result of the workshop can measure, then it is zero almost every- (somewhat simplified) be summarized where. Current-density functional as follows: A general framework of theory admits only the first partial the Hohenberg-Kohn theorem was Hohenberg-Kohn result HK1. deconstructed into what was labelled HK1 and HK2. It turned out that all known results where the Hohenberg- Kohn theorem can be proven follow this structure, and maybe more

Hylleraas annual report 2017 | 2018 45 Meetings and Events –

Tamar and Arieh Warshel From left to right: Nobel laureate Prof. Arieh Warhsel, Hylleraas co-director Kenneth Ruud, Stig Slørdahl (member of the University Board of UiT).

Mini-Symposium in Honour of Nobel Laureate Prof. Arieh Warshel

UiT The Arctic University of Norway, September 25 2018

In connection with the promotion Prof. Arieh Warshel was together with are methods that are much used and of Naubel Laureate Prof. Arieh Martin Karplus and Michael Levitt further developed at the Hylleraas Warshel as Doctor Honoris Causa awarded the 2013 Nobel Prize in chem- Centre. Prof. Warshel has over the years istry for "the development of multi- been a strong supporter of the CTCC at UiT The Arctic University of scale models for complex chemical and Hylleraas Center at UiT, and have Norway, Prof. Kenneth Ruud systems”. Prof. Warshel is one of the visited UiT on multiple occasions, both and Prof. Bjørn Olav Brandsdal most prominent researchers in the field as a lecturer and as an opponent at PhD organized a mini-symposium on of computational methods for studies of defenses. He was also the 2015 Alm- September 25 2018 with former chemical and biological systems. These löf-Gropen lecturer. students and post doctoral fellows of Prof. Warshel. –

Hylleraas annual report 46 2017 | 2018 Meetings and Events –

Speakers at the minisymposium Frontiers in Density-Functional Theory. Left: Prof. Paola Gori–Gorgi. Right: Ass. Prof. Emmanuel Fromager

Minisymposium: Frontiers in Density-Functional Theory

Hylleraas Centre, University of Oslo, November 1 2018

Research into the fundamentals On November 1 2018, the minisym- tree–Fock theory, followed by Ass. Prof. of density-functional theory is an posium Frontiers in Density-Functional Emmanuel Fromager from Université important part of the research at Theory was held at the Hylleraas Centre de Strasbroug in France, whose title in Oslo with two prominent speakers was Unified formulation and optical gap the Hylleraas Centre. In November in the field of density-functional theory. problems in density-functional theory. 2018, two prominent researchers Professor Paola Gori–Giorgi from Vrije in the field presented their recent Universiteit Amsterdam in the Nether- work at a minisymposium in Oslo. lands spoke about the Strong-Interaction – limit of an adiabatic connection in Har-

Hylleraas annual report 2017 | 2018 47 Meetings and Events –

21st National Meeting of the Norwegian Chemical Society

Norway Trade Fairs, Lillestrøm October 16–18 2018

At the National Meeting of the ised the two plenary sessions covering Norwegian Chemical Society in broad topics within chemistry, while Lillestrøm in October 2018, the Hylleraas PI Professor Thomas Bondo Pedersen was a member of the scientific lively sessions of the Division for committee organising the three sessions Quantum Chemistry and Model- of the Division for Quantum Chemistry ling were attended by representa- and Modelling. The Hylleraas Centre tives of all institutions in Norway also provided direct financial support with research into theoretical for the latter sessions. chemistry. – The Division for Quantum Chemistry and Modelling was established within the Norwegian Chemical Society on the Members and affiliates of the Hylleraas initiative of the predecessor of the Hyl- Centre were involved in the organisa- leraas Centre, the Centre for Theoretical tion of the 21st National Meeting of the and Computational Chemistry, in 2007. Norwegian Chemical Society on October The annual meeting of the division also 16–18, 2018, in Lillestrøm. Hylleraas serves as one of two annual meetings Affiliate Professor Einar Uggerud organ- of the Hylleraas Centre and is particu-

Hylleraas annual report 48 2017 | 2018 Organizer Prof. Knut Fægri speaking to members of the Division for Quantum Chemistry and Modelling at the farewell dinner at Restaurant Fratelli, Lillestrøm

larly important for strengthening ties • Prof. Andreas Grüneis, structural dynamics of RNA. Molecular and fuelling collaborations between Technical University of Vienna, dynamics also was at the heart of de researchers at the Hylleraas Centre and Austria Wijn’s talk on the importance of na- researchers in the same field from other • Dr. Vincent Liégeois, noscale friction of adsorbates, while Norwegian institutions. University of Namur, Belgium Hopmann spoke about validation of computed reaction mechanisms. The 15 • Prof. Giovanni Bussi, The sessions of the Division for Quantum additional presentations, mainly given SISSA, Italy Chemistry and Modelling were attended by students and young researchers at by 36 researchers from institutions • Prof. Astrid de Wijn, Norwegian institutions, bear testimony across Norway and included presenta- NTNU, Norway to the great potential of the Norwegian tions within five main topics: electronic- • Assoc. Prof. Kathrin Hopmann, quantum chemistry and modelling com- structure theory, multiscale modelling, Hylleraas Centre, UiT, Norway munity. spectroscopy, biological systems and materials, and catalysis. A total of 20 Grüneis spoke about coupled-cluster scientific presentations were delivered, theory for solids and surfaces, Liégeois mainly by PhD students and postdocs about induced currents and , at Norwegian institutions but also by and Bussi about experiments and the following 5 invited speakers: molecular dynamics simulations of the

Hylleraas annual report 2017 | 2018 49 Outreach –

Hylleraas annual report 50 2017 | 2018 Poster for the Hylleraas Day used at information screens on Campus UiO and Facebook, in addition to emails and on the web pages of Litteraturhuset. The original illustration was bought on Colour- box and edited by Hylleraas Communica- tion Officer Elina Melteig.

The Hylleraas Day 2018 – an outreach event for the general public

The first Hylleraas Day was held partment of Chemistry at the University tists at the Hylleraas Centre have asked at Litteraturhuset in the centre of Oslo, by posters at the UiO campus, themselves. The Hylleraas scientists of Oslo in November 2018. Four and as a Facebook event (but without use computational and mathematical paid advertisement). The poster is re- tools to find the answers, in some cas- presentations of popular science produced in Figure 1. es in collaboration with experimental and a panel discussion, targeting chemists. People often do not realise the the general public, highlighted What if … When scientists are impact computational science can have ongoing research at the Hylleraas driven by curiosity only in experimental fields, and this is also Centre. What would scientists investigate if why both the poster and the text hint – they could investigate anything they at computation and the opportunities wanted? This was the question that that come from it. The Hylleraas Day 2018 took place in advertised the event. The intention the evening of Monday, November 19, was to trigger the curiosity and im- Speakers at Litteraturhuset in Oslo and was or- agination of the audience, and also • Professor Bjørn Olav Bransdal ganised as four popular science lec- to increase awareness of the nature (UiT) Cold adaptions tures delivered by PIs of the Hylleraas and importance of basic research. Is • Professor Kenneth Ruud (UiT) Centre. Roughly forty people attended chemistry the same everywhere in the Relatively good chemistry the event, which was announced three universe? What makes some species • Professor Trygve Helgaker (UiO) weeks earlier by email to everyone at adapt to cold conditions in which their Extraterrestrial chemistry the Department of Chemistry, by email cells "should not" work? Can chemical to teachers that are in regular contact production be sustainable? These are • Professor Odile Eisenstein (UiO) with the School Laboratory at the De- examples of questions that the scien- Sustainable chemistry via a modelling approach

Hylleraas annual report 2017 | 2018 51 Outreach –

Did you think?

When you see a little girl – do you think she will become a math- Hopmann designed the exhibition ‘Did ematician or a quantum chemist? The exhibition ‘Did you think?’, you think?’. Initially, this exhibition organized by Hylleraas PI Assoc. Prof. Kathrin H. Hopmann and PhD showed 15 women working in STEM subjects, each woman holding an item student Karen O. H. Dundas, encouraged the audience to consider relevant to her profession. In addition, their own expectations regarding career choices of females. a childhood picture was shown on the – roll-up (Figure 1). The exhibition was displayed for two weeks in the town hall of Tromsø in March 2018 and also Too few female role models graduate levels in many disciplines, online, as part of the UiT 50 year anni- in chemistry there tends to be fewer and fewer wom- versary [2a]. In September 2018, Dundas and Hopmann extended the exhibition Females are strongly underrepresented en as one climbs up the career ladder. with several roll-ups featuring leaders, in leading positions in STEM subjects This may be caused by many different professors, masters, and natural scien- such as Chemistry (STEM = Science, reasons – among them that females are tists (see the information folder at [2b]). Technology, Engineering and Math- less likely to choose an academic career In total 22 roll-ups were shown for two ematics). In Germany, only 10% of in STEM subjects, for example, because weeks in the shopping mall Nerstranda chemistry professors are women [1]. they lack relevant role models. in Tromsø. Both exhibitions received In Sweden, 18% of professors in natu- much attention, with media coverage ral sciences are women [1b], whereas The ‘Did you think? Exhibition and visits by school classes [3]. Two in Norway, there are 29% female pro- In light of the lack of female role mod- newspaper comments were written, fessors averaged over all disciplines els, it may be relevant to boost the inspired by the exhibition [4]. Hopmann [1c]. Although gender balance has been visibility of women working in the received the UiT Equality Prize for 2018, reached at the undergraduate and STEM fields. With this in mind, in part for this exhibition.

Hylleraas annual report 52 2017 | 2018 From the exhibition ‘Did you think?’.

References: 1 a) K. Zeitler. Book Review European Women in Chemistry, Angew. Chem. Int. Ed., 2011, 50, 9786, b) S.C.L. Kamerlin Where are the female science professors? A personal perspective, F1000Res, 2016 5, 1224, c) dbh.nsd. uib.no/statistikk. 2 a) uit.no/50/trodde-du, b) uit.no/Con- tent/596051/cache=1538382523000/ Front page of Trodde_Du.pdf ‘Did you think?’ 3 a) iTrømso article: https://www. information itromso.no/nyheter/2018/03/08/Utfor- folder drer-stereotyper-om-kvinners-karri- erevalg-16240039.ece , b) Interview with Hopmann: http://kifinfo.no/ nb/2018/03/hedrer-kvinnelige-forsk- ere-i-ny-utstilling, c) UiT article: https:// uit.no/nyheter/artikkel?p_document_ id=565046&p_dim=88208 4 a) http://nordnorskdebatt.no/article/ trodde-du-naturvitenskap, b) http:// nordnorskdebatt.no/article/trodde-du

Hylleraas annual report 2017 | 2018 53 Ph.D. Defenses 2018 –

Hylleraas annual report 54 2017 | 2018 Marius Kadek –

University: UiT The Artic University of Norway Date: 28 August 2018 Thesis: Advancing relativistic electronic structure methods for solids and in the time domain Trial Lecture: Machine learning approaches in electronic structure theory Supervisors: Prof. Kenneth Ruud Dr. Michael Repisky Committee: Prof. Lucas Visscher, Vrije Universiteit Amsterdam, The Netherlands Prof. Lorenzo Maschio, University of Torino, Italy Assoc. Prof. Jana Jagerska, UiT The Artic University of Norway

Sarah Reimann –

University: University of Oslo Date: 2 November 2018 Thesis: Treatment of magnetic fields in density-functional theory Trial Lecture: The strong correlation problem in density-functional theory Supervisors: Prof. Trygve Helgaker Dr. Ulf Ekström Dr. Alex Borgoo Committee: Ass. Prof. Emmanuel Fromager, Université de Strasbourg, France Prof. Paola Gori-Giorgi, Vrije Universiteit Amsterdam, The Netherlands Dr. David Balcells, University of Oslo

Raphael Mathias Peltzer –

University: University of Oslo Date: 6 December 2018 Thesis: Multi-scale computational modelling of bio-chemical systems in the condensed phase Trial Lecture: Modelling reaction rates in biological systems Supervisors: Prof. Michele Cascella Prof. Thomas Bondo Pedersen Prof. Trygve Helgaker Committee: Prof. Mauricio D. Coutinho-Neto, Universidade Federale do ABC, Brazil Dr. Alessandra Magistrato, Italian Research Council c/o SISSA, Trieste, Italy Prof. Mats Tilset, University of Oslo

Hylleraas annual report 2017 | 2018 55 Interview –

Interview with Visiting Scientist

Professor David J. Tozer Durham University, UK –

Professor David J. Tozer, Durham University, UK is a long-term collaborator with scientists at the Hylleraas Centre. He visited the CTCC regularly during its ten years of existence and has already visited the Hylleraas Centre twice. Tozer received his PhD from the University of Cambridge in 1994 and joined Durham University as a lecturer in 1998, where he advanced to reader in 2005 and to professor in 2009. His research focuses on density-functional theory, to which he has made a number of important con- tributions, including the development of new exchange-correlation functionals.

Why did you choose to visit the became a regular visitor over subse- connection. My short visits to the Hyl- Hylleraas Centre and how did you quent years, collaborating with Trygve, leraas Centre in 2017 and 2018 have learn about the Centre and its together with others members of the enabled us to get together and focus visitors program? Centre, notably Andy Teale and Alex our thoughts on this project and move it Borgoo. I was delighted to learn of the forward. The project has also benefited My link to the Hylleraas Centre in Oslo establishment of the Hylleraas Centre in from the wide network of researchers dates back to 2003, when I started col- 2017 and I was fortunate to visit during associated with the Hylleraas Centre, laborating with Trygve Helgaker on both 2017 and 2018 to continue these notably the recent computational input the calculation of shielding constants collaborations. from Toru Shiozaki. and indirect nuclear spin-spin coupling constants in density functional theory In what way was the stay at the How did you find the working (DFT). Trygve informed me about the Hylleraas Centre important for conditions and social and scien- visitor program to the (then) Centre for your scientific activities? tific environment at the Hylleraas Theoretical and Computational Chem- Centre? istry and I recognised that it provided For a number of years, Trygve, Andy, a superb opportunity to develop our Alex, and I have had an interest in the The Hylleraas Centre provides a com- collaboration and to network with oth- definition of static correlation within plete escape from day-to-day work er researchers. I visited in 2003 and DFT and its relationship to the adiabatic distractions, enabling one to focus

Hylleraas annual report 56 2017 | 2018 Prof. David Tozer (left) enjoying a pint with Hylleraas members Andrew Teale and Trygve Helgaker at Oslo Mikrobryggeri in August 2018.

exclusively on research in a friendly, How did you find Norway in hosts and we have enjoyed spending well equipped, and scientifically stimu- general and Oslo in particular? time with them exploring the areas in lating environment. The members of the and around Oslo. After our 2018 visit, Centre have a diverse range of exper- my family and I went further afield, Oslo is lovely. It's a friendly and wel- tise and so discussions can lead to key taking the spectacular train journey coming city with an enormous range new insight into scientific problems; across to Bergen. We really look for- of things to see and do. My wife and there is always someone interesting ward to our next visit to Oslo! my son have visited with me on many to talk to in the coffee room! There is occasions and they have spent their a vibrant seminar programme, with days exploring Oslo's museums, galler- videoconferencing between Oslo and ies, parks and historic sites. They have Tromsø, providing visitors with the also gained an extensive knowledge of opportunity to both attend seminars Oslo's public transport system, while and present their own research. At a visiting its outlying forests, lakes, and social level, members join each other ski trails. In fact, my son has enjoyed for lunch and there is, of course, the the visits so much that he has taught occasional visit to Valka or Oslo Mikro- himself Norwegian! He says 'vi feirer til bryggeri (although first-time visitors og med 17. mai hjemme her i England!' should brace themselves for the price Trygve and his family have been super of a beer!).

Hylleraas annual report 2017 | 2018 57 Visitors –

Visitors in Oslo 2017

Dr. Anand Thirumalai DigiPen Institute of Technology, USA 4–18 August Dr. Hélène Bolvin Université Toulouse III-Paul Sabatie, France 15 August–31 December MSc. Megan Mohadjer Beromi Yale University, USA 15 August–15 November MSc. Ken Alexander Schäfer Johannes Gutenberg Universität Mainz, Germany 1 September–30 November Prof. Jack Simons The University of Utah, USA 4–6 October Ansgard Iring Pausch Karlsruhe Institut für Technologie, Germany 15 October–15 December Prof. David Tozer Durham University, UK 29 October–4 November Prof. Georg Diezemann Johannes Gutenberg Universität Mainz, Germany 8–12 November Dr. Antonio Pizzirusso University of Salerno, Italy 14 November–15 Desember Elisa Rebolini Institut Laue–Langevin Grenoble, France 23 November–3 December

Visitors in Oslo 2018

Dr. Hélène Bolvin Université Toulouse III-Paul Sabatier, France 1 January–30 July MSc. Julie Heron Pierre and Marie Curie University Paris, France 1 February–30 July Dr. Luca Grisanti SISSA di Trieste, Italy 7–12 February MSc. Ken Schäfer Johannes Gutenberg Universität Mainz, Germany 22–25 February MSc. Till Sven Nils Kirsch Johannes Gutenberg Universität Mainz, Germany 25 February–12 March Dr. Taku Onishi MIA University, Japan 2–16 march Dr. Anand Thirumalai DigiPen Institute of Technology, USA 23–31 March Prof. Peter Schwerdtfeger Massey University, New Zealand 6 April Dr. Örs Legeza Wigner Research Centre for Physics, Hungary 16 April Prof. Agustí Lledós Universitat Autònoma de Barcelona, Spain 17–22 April Prof. Walter Thiel Max-Planck-Institut für Kohlenforschung, Germany 13–17 May Dr. Dan Johan Jonsson UiT, The Arctic University of Norway, Norway 14–16 May Dr. Tatjana Skrbic University Ca' Foscari, Venice, Italy 18–26 May Prof. Achille Giacometti University Ca' Foscari, Venice, Italy 18–26 May Prof. Jürgen Gauss Johannes Gutenberg Universität Mainz, Germany 18 May Dr. Lasse Kragh Sørensen Uppsala University, Sweden 27–31 May Dr. Susi Samuli Lethola University of Helsinki, Finland 6 June–31 July Prof. Ludwik Adamovicz The University of Arizona, USA 29 June–13 July Dr. Andrew Michael Teale University of Nottingham, UK 3–10 August Prof. David Tozer Durham University, UK 5–13 August MSc. Jakob Schneider Forschungszentrum Jülich, Germany 10–17 August Dr. Piotr Stefanowicz University of Wroclaw, Poland 14 -21 September MSc. Sebastián Franco-Ulloa Italian Institute of Technology, Italy 19 September–31 December Prof. Andreas Grüneis Technische Universitaet Wien, Austria 14–17 October Dr. Jonathan Smith Temple University, USA 25 October–31 December

Hylleraas annual report 58 2017 | 2018 MSc. Till Sven Nils Kirsch Johannes Gutenberg Universität Mainz, Germany 26 October–2 November Dr. Alex Borgoo Business & Decision, Belgium 1–3 November Dr. Andrew Michael Teale University of Nottingham, UK 16–23 November Prof. Mauricio D. Coutinho Neto Universidade Federal do ABC, Brazil 1–14 December Dr. Alessandra Magistrato CNR Trieste, Italy 4 -7 December Dr. Elisa Rebolini Institut Laue–Langevin Grenoble, France 6–14 December

Visitors in Tromsø 2018

MSc. Willem Jespers Uppsala University, Sweden 28–30 January Lukas Konecny Comenius University in Bratislava, Slovakia 2–12 February Dr. Jaime Rosal Royal Institute of Technology, Sweden 5–9 February Dr. Elke Fasshauer Aarhus University, Denmark 5–9 February Dr. Simen Reine Hylleraas Centre, University of Oslo, Norway 5–9 February Dr. Daniel Friese Heinrich Heine University, Düsseldorf, Germany 5–9 February Dr. Roberto Di Remigio Virginia Tech. Blacksburg, Virginia, USA 5–9 February Prof. Johan Åqvist Uppsala University, Sweden 19–23 March MSc. Louise Poutot Université de Franche-Comté, France 6 April–20 June Prof. Olga Tschaikovskaya Tomsk State University 29 April–3 May Dr. Vladimir Pomogaev Tomsk State University 29 April–3 May Prof. Ivan Konov Tomsk State University 29 April–3 May Prof. Alexei Kononov St.Petersburg State University 30 April–3 May Prof. Yury Kistenev Tomsk State University 29 April–1 May Prof. Walter Thiel Max-Planck-Institut für Kohlenforschung, Germany 15–16 May Prof. Pawel Kozlowski University of Louisville, USA 25 May–25 June MSc. Maksymilian Karczewski Polish Academy of Sciences, Poland 10–17 July Dr. Hugo Gattuso University of Liège, Belgium 14–21 July M.Sc. Pooria Farahani Royal Institute of Technology, Sweden 4–6 September Prof. Arieh Warshel University of Southern California, USA 24–27 September Assoc. Prof. Andrej Antusek Comenius University in Bratislava, Slovakia 22 October–2 December Prof. Johan Åqvist Uppsala University, Sweden 12–16 November Prof. Michele Cascella Hylleraas Centre, University of Oslo, Norway 13–13 November Assoc. Prof. Swapan Chakrabarti University of Calcutta, India 2–15 December

Hylleraas annual report 2017 | 2018 59 Externally Funded Projects –

Hylleraas annual report 60 2017 | 2018 The financial support the Hylleraas Centre receives as a Centre of Excellence from the Research Council of Norway and from its host institutions constitutes a long-term secure funding allowing us to develop and pursue research projects that require a sustained effort over years. However, to reach the ambitious goals of the centre, additional funding is needed — to focus on particular research challenges and to pursue promising new research directions that may arise in the course of the work at the centre. In the following, we present the external research grant proposals that have been approved for funding during the report period. Progress in these projects will in the future be reported as part of the activities of the research themes.

Hylleraas annual report 2017 | 2018 61 Externally Funded Projects –

A Topological Approach to Density-Functional Theory (topDFT)

Andy Teale (University of Nottingham and UiO) – ERC Consolidator Grant, 2018–2023

Hylleraas Adjunct Professor and materials science is a testament This project builds upon research carried Andy Teale was in 2017 awarded to its black-box nature and low cost. out at the Hylleraas Centre on the adiabatic a large €2M Consolidator Grant However, many important areas remain connection in DFT [1]. This tool allows inaccessible to DFT simulations, includ- for the characterization of correlation (CoG) from the European Re- ing applications to strongly correlated as weak or strong by studying how the search Council (ERC). The ERC materials and systems in strong elec- energy of a system changes as the elec- CoG scheme aims to identify and tromagnetic fields. The topDFT project tronic interactions are switched on / off support the very best and cre- will deliver new conceptual approaches by an interaction strength parameter. ative mid-career independent to design the next generation of den- Higher-order dependence on this pa- researchers in Europe via 5-year sity-functional methods. This will be rameter indicates stronger correlation. consolidated funding to pursue achieved by pursuing three parallel In the topDFT approach this concept is ground-breaking frontier research. strategies: i) Developing new strategies brought to a local level (pointwise in for the design of functionals ii) Imple- the molecular system) allowing not only His 5-year project topDFT con- menting topological DFT, a new com- identification of the type of correlation cerns the fundamentals of den- putational framework iii) Developing prevalent in a given system but also sity-functional theory, an active extended density-functional theories. in which regions of the system corre- and lively research area at the lation is strong or weak [2]. This local Hylleraas Centre. To pursue these goals, a new framework information is directly connected to the for computation will be developed by exchange–correlation interactions of – combining techniques from topologi- and can be used to construct cal electronic structure methods with density-functional approximations that DFT — allowing for the identification of more adequately adapt to the nature Density-functional theory (DFT) is the correlation ‘hotspots’. By recognising of the interactions present in different most widely used method to study the these hotspots and adapting dynami- regions of a molecule [3]. electronic structure of complex mol- cally to them, we will develop new ap- ecules, solids, and materials. Its use proximations with substantially greater across chemistry, solid-state physics accuracy.

Hylleraas annual report 62 2017 | 2018 Externally Funded Projects –

The correlation energy density for the N2 molecule (left panel) and, its decomposition into weakly and strongly correlated regions (right panel)

The different regions of interest are neatly delimited by topological features of the electron density (particularly the Laplacian of the density) and this allows for the more controlled application of high order models where required, pre- venting spurious contributions from these terms in regions where stand- ard DFAs are already adequate. This decomposition is illustrated for the N2 molecule in the figure. These models are readily applied to extended DFT frameworks such as current-density- functional theory for molecules in strong electromagnetic fields, and ensemble DFT for molecules with near degenerate electronic configurations. The topDFT project will open the way to Local adiabatic connections, to be described a new generation of density-functional by density-functional approximations. approximations that enable the study strongly correlated molecules and ma- terials in the presence of strong elec- References: tromagnetic fields. 1 A. M. Teale, S. Coriani and T. Helgaker, 3 S. Vuckovic, T. J. P. Irons, A. Savin, J. Chem. Phys., 2009, 130, 104111; A. M. Teale and P. Gori-Giorgi, The total budget for the project is €2M. 2010, 132, 164115. J. Chem. Theory Comput., 2016, 12, 2 T. J. P. Irons and A. M. Teale, Mol. Phys. 2598. 2016, 114, 484.

Hylleraas annual report 2017 | 2018 63 Externally Funded Projects –

The Nordic Consortium for

CO2 Conversion (NordCO2)

Kathrin Hopmann (UiT) and Ainara Nova (UiO) – NordForsk Nordic University Hubs, 2018–2023

The Hylleraas Centre is applying consortium (site.uit.no/nordco2) com- Advisory Board (EAB). In 2018, two PhD computational methods to develop prises computational and experimental courses with around 25 participants, a sustainable solutions for the chemists working with homogeneous, kick-off meeting (35 participants) and heterogeneous, electrochemical, and a CO outreach day (several hundred chemical industry. Hylleraas PI 2 photochemical approaches to develop visitors) were organized. Assoc. Prof. Kathrin H. Hopmann catalysts for conversion of CO2 to has successfully initiated the chemicals and fuels. The consortium Hylleraas members in NordCO2 Nordic Consortium for CO is funded by a NordForsk University 2 Assoc. Prof. Kathrin H. Hopmann (NordCO Hub grant [1], with financing from 2018. 2 Conversion, comprising nine leader), Senior Researcher Ain- If the midterm evaluation in 2020 is universities. Hylleraas senior ara Nova (NordCO PI and SC mem- passed, the consortium will be financed 2 researcher Dr. Ainara Nova heads ber), Prof. Odile Eisenstein (Member until 2023. one of the research groups in of the NordCO2 EAB), Prof. Michele NordCO . Cascella (NordCO collaborator) and 2 Activities in NordCO 2 – 2 several PhD students, postdocs The goal of NordCO2 is to establish an and researchers, including Lluis Artus, internationally leading research and Julie Heron, Marc Obst, Ljiljana Pavlovic, When the oil runs out training environment on chemical Anders Brakestad, Diego Garcia-Lopez, Currently both energy-storage mole- conversion of CO2 to chemicals and fuels. and Torstein Fjermestad. cules (such as fuels) and chemicals This is achieved through strengthening (such as pharmaceuticals, solvents, the collaborations between excellent References: additives) are produced from com- Nordic research groups in the field, cou- 1 nordforsk.org/en/programmes-and-pro- pounds that derive from oil. In the pled with meetings, joint PhD courses, jects/programmes/nordic-university-hubs quest for alternative feed summer schools and a Nordic Exchange stocks, a significant attention is being Program (NEP) for students. The activities devoted to develop catalysts that can in NordCO2 are overseen by a Steering convert the abundant waste molecule Committee (SC) with members from all

CO2 into useful chemicals. The NordCO2 involved universities and an External

Hylleraas annual report 64 2017 | 2018 Participants at the NordCO2 kick-off meeting May 2018.

UiT - The Arctic University of Norway University of Iceland (Uol)

Uppsala University University University of of Oslo (UU) Helsinki Bergen (UiB) (UiO) University (HU)

Stockholm University Aarhus (SU) University (AU) Royal Institute of Technology (KTH)

Nine Nordic universities are part of NordCO2. Ainara Nova enjoyed lecturing at the PhD course

For all research groups, see site.uit.no/ ‘Mechanisms for CO2 Activation’ September 2018. nordco2.

Hylleraas annual report 2017 | 2018 65 Externally Funded Projects –

Evolutionary Principles of Biocatalysts from Extreme Environments

Bjørn Olav Brandsdal (UiT) – RCN FRIPRO Toppforsk 2018–2023

Prof. Bjørn Olav Brandsdal was in 2018 granted a Toppforsk project by the Research Council of Norway entitled Evolutionary Principles of Biocatalysts From Extreme Environments. The project period is for five years with a budget of 29.9 MNOK (12.5 MNOK from RCN and 17.4 MNOK from UiT). Hirings made in 2018 were: Dr. Bjarte Aarmo Lund for a three year post doctoral position (September 2018), Dr. Geir Villy Isaksen as a senior researcher and Prof. Johan Åqvist as Prof. II (20% position) for five years (both from November 2018). The project will announce two PhD position and one post doctoral position (three years) in 2019, and finally one post doctoral position in 2020 (three years). –

Life in the cold requires such harsh conditions. Clearly, these specialized organisms have been adapted and op- Extremophiles are organisms capable timized through millions of years of of surviving under harsh environmen- evolution to adjust their cellular com- tal conditions normally regarded as positions and machineries to function incompatible with life. Psychrophiles close to the freezing point of water. But (or cold-loving) species, ranging from our understanding of these adaptations bacteria to invertebrates and deep-sea at a molecular level remains elusive. and polar fishes, are extremophiles that The project will focus on evolutionary are able to colonize and survive under principles behind adaptation to extreme

Hylleraas annual report 66 2017 | 2018 environments with emphasis on how dustrial and biotechnological point of Figure 1: Computational Arrhenius temperature affects the stability and view, due to their potential use as bio- plots using Empirical Valence Bond activity of enzymes and ribosomes. catalysts either in their natural form simulations reveal the underlaying or in engineered variants. This is be- energetics of the enthalpy-entropy compensation in enzymatic temperature cause their activity has been tailored Computer simulations unravel adaptation. adaptational strategies through evolution to meet and function Computationally, this requires that we efficiently in unusual conditions. These can connect the underlying microscopic biocatalysts can either be extracted di- energetics of the macromolecular rectly from extremophilic species or structures with macroscopic observa- reengineered, given that the design bles using computational approaches principles of the desired biophysical pioneered by Brandsdal and Åqvist properties are known. (Figure 1). The contribution to the free energy from enthalpy and entropy re- For more information, please visit: http://site.uit.no/cube/ mains highly challenging to calculate, particularly when dealing with large References: complex biological 1 J. Åqvist, G. V. Isaksen, and B. O. involved in catalysis and binding events. Brandsdal, Nat. Chem. Rev. 2017, 1, The core activities are centered on a 0051. suggested hypothesis of how evolu- tion changes the enthalpy-entropy balance to allow enzymes to function near the freezing point of water, as discussed in our recent publication in Nature Reviews of Chemistry [1]. The interest in enzymes from extremo- philes is also immense from an in-

Hylleraas annual report 2017 | 2018 67 Externally Funded Projects –

Multi-Resolution Methods Including Quantum Chemistry, Force Fields, and Hybrid Particle-Field Schemes

Michele Cascella (UiO) and Jürgen Gauss (University of Mainz) – German Research Foundation 2018–2023

The project Multi-resolution methods including quantum chemistry, In the project Multi-resolution methods force fields, and hybrid particle-field schemes by Hylleraas member including quantum chemistry, force Michele Cascella together with Jürgen Gauss from the University of fields, and hybrid particle-field schemes, Hylleraas PI Michele Cascella and Prof. Mainz has been approved by the German Research Foundation as part Jürgen Gauss, University of Mainz, of the Collaborative Research Centre/Transregio TRR 146 Multiscale Germany, will tackle this fascinating Simulation Methods for Soft-Master Systems, which will receive about problem. The aim is to establish a 9 million EUR for the next four years. The project will involve the general protocol able to describe how collaboration of two PhD students (one from Mainz, one from Oslo) local chemical changes propagate at to develop flexible tools allowing multi-scale simulations for very much larger dimensionalities. Possible large systems adopting the most appropriate methods required by applications are very wide, involving, the systems under investigation. for example, biochemical signal trans- duction, membrane remodelling, smart – materials, etc.

Multi-scaling techniques where chem- The project is funded by the German ical moieties are described at a quan- Research Foundation, within the Trans- tum (QM) level are embedded into an regional Collaborative Research Centre environment represented by simplified TRR-146 Multiscale Simulation Methods molecular mechanics (MM) potentials for Soft-Matter Systems shared by the are well established computational tools University of Mainz and the Max- used in the treatment of complex chem- Planck Institute for research ical and biochemical systems. While in Mainz, and the Technical University such hybrid QM/MM schemes are now- of Darmstadt. This project establishes adays routinely used, significantly less an important collaboration between the work has been done toward the cou- Hylleraas Centre and an international pling with coarser descriptions, toward excellence centre partner. the mesoscale dimensionality.

Hylleraas annual report 68 2017 | 2018 Externally Funded Projects –

Digital Discovery of Antimicrobial Molecules from Marine Artic Resources with Reduced Risk of Triggering Resistance (DigiBiotics)

Kenneth Ruud (UiT) and Bjørn Olav Brandsdal (UiO) – RCN Digital Life Program, 2018–2023

Prof. Kenneth Ruud and Prof. Figure 1: No new classes of antibiotics Bjørn Olav Brandsdal are PIs in have been developed the proposal Digital discovery in the past 30 years. of antimicrobial molecules from marine Arctic resources with reduced risk of triggering resist­ ance (DigiBiotics), which in 2017 received funding from the Digi- tal Life program in the Research develop novel experimental and com- developing theoretical methods for fast Council of Norway. putational methods for determining and accurate assignment of molecular – molecular structure and dynamics. This structure including determination of will allow for a better understanding absolute configuration and mapping Antimicrobial resistance is currently of peptide-membrane interactions and of conformational space. Prof. Brands- causing around 700 000 deaths annual- provide an atomic basis for the devel- dal the work package where the ly, with an estimated rise to 10 million opment of new drug targets. Promis- interactions between medium-sized over the next 30 years. All antibiotics ing compounds will be refined to com- compounds and biological membranes available for use in patients today are pounds acceptable for industrial drug are examined. derived from a few classes discovered development. The project will collab- before the mid-1980s (Figure 1). Con- orate with AstraZeneca and AmiCoat The DigiBiotics project started in tinuous development of antimicrobial and also international research groups. January 2018 for a five year period. compounds with new modes of action The total budget for the project is is essential to reduce the risk posed by Molecular structure and dynamics of 50 MNOK where 20 MNOK is from the antimicrobial resistance. DigiBiotics new natural as well as synthetic will be Research Council and 30 MNOK from will contribute to meet this challenge examined in two work packages with- UiT The Arctic University of Norway. by developing new compounds inspired in the DigiBiotics project. Prof. Ruud The project leader is Prof. John Sigurd by marine Arctic natural products and leads a work package that focuses on Svendsen from the Department of Chemistry (UiT).

Hylleraas annual report 2017 | 2018 69 Externally Funded Projects –

A Posteriori Error Estimates for Coupled-Cluster Theory

Fabian Faulstich (UiO), Simen Kvaal (UiO), and Lin Lin (UC Berkeley) – Peder Sather Center for Advanced Study, UC Berkeley 2018–2019

Error control is an important but Dr. Simen Kvaal (UiO) together with With its interdisciplinary nature, this often overlooked aspect of com- Assoc. Prof. Lin Lin (UC Berkeley) re- project furthers the impact of mathe- putational studies of molecules. ceived funding from The Peder Sather matics in theoretical chemistry, which Center for Advanced Study for the pro- is a relatively young but upcoming field. The project A Posteriori Error Esti­ ject A Posteriori Error Estimates for Coupled- Aside from the cutting-edge research, mates for Coupled-Cluster Theory Cluster Theory. The aim of this project this project aspires to foster the develop- aims to establish a more direct is to study the use of local numerical ment of new research collaborations be- approach to error control, in a basis sets to provide a mathematically tween the Hylleraas Centre for Quantum collaboration of the Hylleraas sound error control in quantum chem- Molecular Sciences and research groups Centre with researchers at UC ical calculations. The field of applied at UC Berkeley. To that end, Kvaal’s PhD Berkeley. mathematics provides a rich selection student Fabian M. Faulstich conducted – of numerical basis sets for different research at UC Berkeley from Septem- purposes. Most of these ‘mathematical’ ber 2018 to May 2019. The total amount basis sets allow a priori and a posteriori of funding for this project is $22,250. error analyses, providing a new and more direct approach to error control of quantum chemical calculations.

Hylleraas annual report 70 2017 | 2018 Externally Funded Projects –

Error Estimates for Coupled-Cluster Methods, Ground and Excited States

André Laestadius (UiO) – RCN FRINATEK Young Research Talent (YRT) Grant, 2019–2023

The RCN YRT Grant Error Esti­ Dr. Andre Laestadius has received It has also the possibility to offer new mates for Coupled-Cluster Meth­ funding from the RCN for the project insights concerning the practical use ods, Ground and Excited States Error estimates for coupled-cluster meth- of these methods. ods, ground states and excited states. This enables Dr. Andre Laestadius research project aims at improving The proposed research is interdis- to establish his own, independ- the understanding of excited states ciplinary, combining mathematics, ent research group at the Hyl- in quantum chemistry by providing physics and chemistry. It will be carried leraas Centre, contributing to (i) a mathematical analysis of excited out at the Hylleraas Centre for Quantum the mathematical foundation of states, and (ii) a detailed analysis of Molecular Sciences in close collabo- coupled-cluster theory in general approximation errors since the exact ration with Dr. Simen Kvaal and Prof. and error estimates in particular. solutions are never obtained in prac- Thomas Bondo Pedersen, as well as – tice. Furthermore, the objective of the international researchers includ- project is to establish quantitative er- ing Prof. Anna Krylov (University of ror estimates that are accessible to the Southern California) and Prof. Jürgen quantum chemistry community. This Gauss (Universität Mainz). The project also includes the development of a cri- will fund a postdoctoral position, with terion, or diagnostic, that guarantees start during 2020. The project starts that a quantum chemical computation in December 2019 and will continue gives a correct solution. The relevance for approximately four years and has of this project lies in providing a sound a budget of 8000 kNOK. mathematical foundation for widely applied methods in quantum chemistry.

Hylleraas annual report 2017 | 2018 71 Externally Funded Projects –

Magnetic Chemistry

Trygve Helgaker (UiO) – RCN FRIPRO Researcher Project 2019–2022

Chemistry in an ultrastrong mag- as strong as the electric forces. Their So far, only small molecules have been netic field is different from that complicated interplay sets up an exotic studied in strong magnetic fields and on Earth, dominated by paramag- chemistry of egg-shaped atoms, dra- such studies have revealed many fas- matically affecting structure and re- cinating and unexpected phenomena netic rather than covalent bond- activity of molecules. In the project such as a new chemical bonding mech- ing, for example. The RCN FRIPRO Magnetic Chemistry, such chemistry anism. In the present project, we target project Magnetic Chemistry allows will be studied theoretically, using larger and more complex systems, the members of the Hylleraas the tools of quantum chemistry. Apart combining studies of energetics with Centre to continue their work on from shedding light on a fascinating molecular dynamics. The development this fascinating chemistry in an chemistry that cannot be experienced of molecular dynamics will enable us extreme environment, extending by us directly, the study of chemistry in to study for the first time the effect of their study to larger systems and ultra-strong magnetic fields has strong magnetic fields on chemical re- experimental relevance in astrophysics. actions. We are, in particular, interested to molecular dynamics. Atomic spectra have for a long time in the stability of larger molecules and – been observed on magnetic white dwarf their decay paths. stars and are used to map the field strength on their surface. Very recently, The Magnetic Chemistry project runs On Earth, chemistry is governed by the the first observation of molecules on from 2019 to the end of 2022, with a Coulomb interactions between electrons nonmagnetic white dwarf stars has total budget of 10 MNOK. Two postdocs and nuclei, the effect of magnetism been made, suggesting that molecules and one PhD student will be hired on being weak and subtle. Elsewhere in also exist on magnetic white dwarf this project. the universe, the situation is different. stars. However, they cannot be detect- On many white dwarf stars, the mag- ed without reliable quantum-chemical netic forces acting on the particles are predictions.

Hylleraas annual report 72 2017 | 2018 Externally Funded Projects –

Optical Probe Sensors at Biological Environments (OPS@BE)

Kenneth Ruud (UiT), Maarten Beerepoot (UiT), Luca Frediani (UiT) and Trygve Helgaker (UiO) – SIU Russia Cooperation Program 2018–2020

Norwegian and Russian students participating in the Computational Chemistry course at UiT The Arctic University of Norway together with some of the principal investigators and project coordinators: Luca Frediani (UiT; back row, far right), Olga Tchaikovskaya (Tomsk State University; center row, number five from the right), Tatiana Sa- vinova (UiT; center row, number three from the right) and Kenneth Ruud (UiT; front row, far left)

The objective of the OPS@BE pro- and develop biological and cooperation between these institutions gram is to build a strong, multi- drugs, together allowing for novel appli- in the field of biophotonics. Experi- disciplinary educational program cations in medicine and pharmacology. mental and theoretical courses open Developing these advanced techniques to international­ students will be estab- to educate students in state-of- requires broad theoretical education in lished at the MSc/PhD levels in each the-art experimental and theo- theoretical, computational and physical country, fully recognised by all part- retical photochemistry, building chemistry in combination with skills in ners. Annual workshops will be organ- on the complementary expertise the practical use of experimental and ised to improve learning outcomes; to of the partners at the Hylleraas computational methods. identify a scope for further integration Centre and Russian institutions. between existing programmes; and to Through student exchange and the develop and strengthen the programme – development joint courses recognised at all partners. by the partners, OPS@BE will improve the quality of the education provided to In 2018, 18 Russian students partici- Single- and multi-photon spectroscopy students in computational and experi- pated in the course KJE-3102 Compu- can provide invaluable insight into the mental biophotonics at the Norwegian tational Chemistry at UiT The Arctic electronic and chemical properties of and Russian partner institutions: UiT University of Norway together with the large molecular structures through The Arctic University of Norway and Norwegian students taking this class. photo-physical and photo-chemical Tomsk State University, with partic- The course was then organized as an processes occurring in the presence ipation of the State University of St. intensive course over a period of two of electromagnetic fields and through Petersburg and the University of Oslo. weeks, with daily lectures and exercise interactions with the environment. This The initiative is based on the common sessions. provides a non-invasive way to monitor interests of the partners, and the joint and control molecular biomarkers, test ambition to establish educational

Hylleraas annual report 2017 | 2018 73 RT Activity Reports –

Hylleraas annual report 74 2017 | 2018 At the Hylleraas Centre, we develop and apply computational methods to under- stand, interpret, and predict new chemistry, physics, and biology of molecules in complex and extreme environments. Our work is organized into six research themes (RTs):

• Electronic Structure (RT1) • Multiscale Modelling (RT2) • Spectroscopic Processes (RT3) • Extreme Environments (RT4) • Chemical Transformations (RT5) • Multiphase Systems (RT6)

Each RT has its own deliverables, directed towards the common goal of the centre. The first two themes, RT1 on electronic structure and RT2 on multiscale modelling, describe matter in isolation, providing the backbone for our work. The next two themes, RT3 and RT4, introduce fields and photons. They are at the heart of the centre, dealing with spectroscopic processes and extreme environ- ments. The tools developed in these four RTs will enable our application themes to address problems that are today beyond the reach of computation. We focus on chemical transformations in RT5 and on multiphase systems in RT6 — areas that, among many other things, aim to secure clean energy and to combat anti- microbial drug resistance.

In the following, the 2017–2018 report is provided for each RT.

Hylleraas Research Themes

Hylleraas annual report 2017 | 2018 75 RT Activity Reports –


RT1: Electronic-Structure Theory

Principal investigators: Thomas Bondo Pedersen and Luca Frediani

Research within RT1 is focused on 2018, Prof. Thomas Bondo Pedersen, cial Crystal and Cryscor programs, the the quantum mechanical descrip- postdocs Gustav Baardsen and Elisa rather counterintuitive conclusion was tion of the electronic structure of Rebolini, and PhD students Audun reached that the most efficient local Skau Hansen and Karl R. Leikanger correlation algorithm is not achieved molecules and solids, with pro- published a paper showing that the with the “best” localised unoccupied jects ranging from the formula- divide-expand-consolidate (DEC) orbitals but with projected atomic orbit- tion and mathematical analysis of framework, originally developed als (PAOs), which are not optimal with novel quantum chemical models for molecules, can be adapted to pe- respect to any definition of locality. The to the development of efficient riodic boundary conditions whilst PAOs, as it turns out, tend to be just suf- open-source software packages. maintaining correlation-energy error ficiently delocalised to capture electron These efforts provide support for control through a single parameter correlation much more efficiently for the research in all other RTs of [1]. The main remaining challenge is ionic, covalent, and molecular materi- bringing down the CPU and memory als than unoccupied Wannier orbitals the Hylleraas Centre. requirements to a level that allows optimised with respect to commonly – routine applications of more advanced used criteria. A manuscript is about to coupled-cluster models to condensed- be submitted in collaboration with Prof. Coupled-cluster theory phase systems. Lorenzo Maschio in Turin, and work for extended systems on further investigations of the new While the idea of exploiting the rapid In practice, exploiting locality requires PAO-based X-DEC implementation for spatial decay of electron-electron single-particle states, occupied and un- more advanced coupled-cluster wave correlations in insulators to formulate occupied orbitals, which are local in functions is progressing, including the efficient local correlation algorithms space but delocalised in energy. Hansen already implemented random-phase dates back to the 1980s, the development has developed a novel stochastic algo- approximation. of reliable black-box algorithms remains rithm for orbital localisation, which a grand challenge in quantum chemis- enables numerical experiments with Multiwavelets different definitions of the concept of try. A black-box algorithm must depend Development of the MRChem code for orbital locality. Using the Python/C++ on as few adjustable parameters as multiwavelet-based density-functional code X-DEC developed by Baardsen, possible and thus provide a simple and theory calculations has been the main Rebolini, and Hansen, and the commer- easy route to error control. In March focus of the group of Assoc. Prof. Luca

Hylleraas annual report 76 2017 | 2018 RT Activity Reports –

Frediani in 2018. Several promising di- ing on the mathematical foundations mechanics that naturally leads to the rections are being explored at present. of multiwavelet theory and its applica- coupled-cluster hierarchy of computa- Dr. Peter Wind and Dr. Stig Rune Jensen tions to theoretical chemistry. Wind tional methods. The BIVAQUM project are working on the code paralleliza- has also worked on a prototype mod- is focused on a mathematical analysis tion which is now able to scale to a few ule for geometrical derivatives to be of bivariational methods and develop- thousand cores and to a system size interfaced to MRChem as well as ment of new computational methods. of several hundred electrons. Gabriel any quantum chemistry code, and In particular, novel attacks on the mul- Gerez is working on his master project in particular the codes developed at tireference problem are being explored. to extend MRChem to deal with sol- the Hylleraas Centre (X-DEC, Dalton, vation within a variational formalism. LSDalton, Dirac, London, to cite a few). In 2018, a mathematical paper on the Magnar Bjørgve has developed a Python extended coupled-cluster method was interface to the MRCPP library, which Bivariational Approximations published, after about a year in review enables us to combine the efficiency and in Quantum Mechanics [2]. An analysis of the non-orthogonal precision of a multiwavelet representa- The ERC Starting Grant project BIVAQUM orbital optimized coupled-cluster meth- tion of functions and operators with the (Bivariational Approximations in Quan- od was published [3], and an analysis of flexibility of Python for proof-of-principle tum Mechanics and Applications to Quan- the coupled-cluster method tailored by testing of new ideas. At the same time, tum Chemistry) entered its fourth year tensor network states (TNS-TCC) was Bjørgve and Jensen have worked on an in 2018. In addition to PI Dr. Simen submitted for publication in collabora- implementation of periodic boundary Kvaal, the group at this point consisted tion with Prof. Reinhold Schneider in conditions in MRChem, which is now of postdocs Rolf Heilemann Myhre and Berlin and Prof. Örs Legeza in Budapest able to run LDA calculations on simple Andre Laestadius, and PhD students [4]. This is the first mathematical anal- cubic . Frediani is working on Fabian Maximilian Faulstich and Bene- ysis of a multireference coupled-cluster extending the linear response function- dicte Ofstad. At the end of 2018, Myhre scheme in the literature, and is current- ality of MRChem to GGA functionals and started a new postdoc fellowship at ly under review. open-shell systems, whereas Anders NTNU, and postdoc Tilmann Boden- Brakestad is working on a large bench- stein was hired, staring early 2019. The A "code laboratory" has been written mark of molecular polariz­abilities at BIVAQUM project is centered around using Python, which is able to auto- the complete basis set limit. Hylleraas the bivariational principle, an uncon- matically derive the complicated alge- affiliate Prof. Tor Flå has been work- ventional formulation of quantum braic expressions needed for solving

Hylleraas annual report 2017 | 2018 77 RT Activity Reports –

the electronic Schrödinger equation to be replaced by a functional that is the open-ended response theory mod- using coupled-cluster theory, and is also differentiable, yet remarkably still ex- ule OpenRSP, as needed for RT3, and able to automatically generate fast code act. Recent work [5] extends the 2014 2) initial work on interfacing the DFT from these expressions. This allows work, which was restricted to standard module of LSDalton to a classical po- benchmarking of novel computational DFT, to a setting that is general enough larisable-embedding framework using schemes developed by the team, and to encompass most generalized density the FraME module, thus contributing several such are currently under in- functional theories. It also enabled a to the goals of both RT2 and RT3. Work vestigation. rigorous analysis of the convergence has also been conducted to establish of a new Kohn-Sham iteration scheme. an interface between the core integral Density-functional theory A follow-up work adapts the approach routines of LSDalton to the one-electron Density-functional theory (DFT) is to current-density functional theory integral module t-Integrals, to enable one of the main settings where quan- and illustrates many of the theoretical support for effective core potentials tum chemists encounter the mathe- concepts by a numerical application to during 2019. This Dalton program suite matical notion of functional deriva- a quantum ring. was released on November 19 with tives. Functional derivatives underlie several minor improvements, ADMM results that are central to practical Linear-scaling technology basis sets and ADMM electric response applications, for example, the Kohn- The LSDalton program has been de- properties, and with preliminary sup- Sham eigenvalue equations. Howev- veloped by members of the Hylleraas port of open-ended response theory for er, functional derivatives are actually Centre and collaborators around the geometric, electric, and mixed geomet- ill-defined in density functional theory world over the last decade and can to- ric-electric properties. Senior Engineer and only in 2014 was a rigorous founda- day be applied to molecular systems Dr. Simen Reine has been the central tion developed by members of the Hyl- consisting of more than 1000 atoms, developer in these efforts. leraas Centre. The rigorous approach is both at the DFT and coupled-cluster based on Moreau-Yosida regularization, levels of theory. The work on LSDal- a standard regularization technique in ton in 2018 has been twofold: 1) im- the literature on convex the ordinary plementation of high-order derivative non-differentiable density functional integrals combined with an interface to

Hylleraas annual report 78 2017 | 2018 Five of the seven delegates from the Hylleraas Centre at Oberwolfach, March 2018. From left: S. Kvaal, F.M. Faulstich, A. Laestadius, T.B. Pedersen, T. Helgaker.

Solid-state modelling that this is not needed except for true Hylleraas Centre is proud to note that A major accomplishment during 2018 linear dependencies, and instead the Faulstich and Laestadius won awards was the completion of an all-electron diffuse functions were found to be very at the 2018 Sanibel symposium. fully relativistic Kohn-Sham DFT meth- important for the accuracy of the re- od for solids based on Gaussian-type sults, with errors as large as 1 eV in References orbitals (GTOs), a work that Marius the band gap occurring if diffuse func- 1 E. Rebolini, G. Baardsen, A.S. Hansen, K.R. Leikanger, and T.B. Pedersen, Kadek defended for his PhD in august tions are removed from the basis set [6]. Equally surprising was the obser- J. Chem. Theory Comput. 2018, 14, 2018 [6]. This work was supervised by 2427-2438. vation that, at the four-component level Dr. Michal Repisky and Prof. Kenneth 2 A. Laestadius and S. Kvaal, of theory, diffuse functions can push Ruud. The approach employed avoids SIAM J. Numer. Anal. 2018, 56, 660- many of the common approximations negative-energy solutions (positronic 683. introduced in solid-state codes and states) into the space of occupied elec- 3 R.H. Myhre, J. Chem. Phys. 2018, 148, which limit their applicability in the tronic solutions, requiring care when 094110. modelling of molecular properties occupying orbitals in order to converge 4 F.M. Faulstich, A. Laestadius, that depend on the electron density the results [6]. S. Kvaal, Ö. Legeza, and R. Schneider, close to the nuclei. A new PhD student, ArXiv:1802.05699. Marc Joosten, is building on this work Workshops and conferences 5 A. Laestadius, M. Penz, E. Tellgren, M. Ruggenthaler, S. Kvaal, and to implement electric field gradients Several workshops and conferences T. Helgaker, J. Chem. Phys. 2018, at the nucleus as well as Mössbauer were attended by the scientists of RT1, 149, 164103. contributing oral presentations and spectroscopy for solids based on a fully 6 M. Kadek, M. Repisky and K. Ruud, relativistic formalism. posters. For example, Tellgren, Kvaal, submitted to Phys. Rev. B, Faulstich, Laestadius, and Pedersen all arXiv:1902.02828. In the modelling of solids using Gaussian- gave oral presentations at the cross- type orbitals, it is conventional wisdom disciplinary workshop Mathematical that diffuse basis functions have to be Methods in Quantum Chemistry at the removed from the basis set to ensure renowned Mathematiches Forschungs­ numerically stable results. Kadek found institut Oberwolfach (Figure 1). The

Hylleraas annual report 2017 | 2018 79 RT Activity Reports –


Multiscale Modelling

Principal investigators: Michele Cascella and Bjørn Olav Brandsdal

From QM to mesoscale, building time enabling high-performance multi- tated by a lightweight communication algorithmic bridges across mul- scale simulations of molecular systems. library (CommLib) which utilizes MPI tiple resolutions. The goal is thus to allow partitioning of intercommunicators, thus giving access a system into several subsystems that to high-speed interconnects, such as – can be treated using different models, InfiniBand and Omni-Path Architecture. ranging from quantum mechanics (QM), over atomistic molecular mechanics The MiMiC framework has so far been (MM) and coarse-graining (CG), to con- used to couple the high-performance 2018 was an important year for RT2, tinuum mechanics (CM). To achieve and versatile programs CPMD and where key projects setting the ground this level of flexibility while maintain- GROMACS to enable electrostatic em- for the research in the next years were ing high efficiency, we used a strategy bedding QM/MM MD simulations. The established. based on a multiple-program multiple- new QM/MM implementation treats data (MPMD) model with loosely coupled long-range electrostatic QM–MM in- MiMiC: a framework for multiscale programs. teractions through the multipoles of modelling in computational Figure 1 the QM subsystem, which substantially chemistry reduces the computational cost without The initial implementation of a flexible Using this strategy, MiMiC couples a loss of accuracy compared to an exact and efficient framework for multiscale main driver, e.g., an MD driver that treatment (Figure 2). This allows highly modelling in computational chemistry propagates the particles in time, to a efficient QM/MM MD simulations of (MiMiC) was completed in late 2018. set of external programs, each of which very large systems. A preprint presenting the framework concurrently compute the contribu- Figure 2 and demonstrating its use for hybrid tions related to a specific subsystem. quantum mechanics / molecular me- The interactions between subsystems chanics (QM/MM) molecular dynamics can be computed by MiMiC in cases (MD) simulations has been deposited on where the functionality is not available ChemRxiv [1]. The aim of the framework in the external programs. The commu- is to facilitate the development of novel nication between programs is facili- multiscale models while at the same

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External MiMiC Main Driver

Subsystem interactions QM, MM, Molecular CG, etc. Dynamics Client CommLib Server

Figure 1: Illustration of the strategy used in the MiMiC framework.

10 2 0 0 1 1 10 3 80 2 2 ] . ] u 4 . 10 3 3 % 60 a [ [

4 4 x M

a 5 5 M 10 / 5 m l M | 40 e Q r g 6 6 t | 10 6 7 7 20 8 8 7 10 9 9 0 24 34 44 54 64 74 24 34 44 54 64 74 Short-range cutoff distance [a.u.] Short-range cutoff distance [a.u.]

Several extensions of the QM/MM The development of the MiMiC frame- Figure 2: Convergence of the forces methodology are currently ongoing, work is headed by Jógvan Magnus in a solvated GB1 (approx. including polarized embedding, treat- Haugaard Olsen at Hylleraas-UiT in 30.000 atoms) with respect to the ment of excited states, and combina- collaboration with Prof. Ursula Röth- short-range cutoff distance and the or- der of the multipole expansion used in tions with multiple time step (MTS) lisberger from EPFL, Switzerland, and the long-range coupling. Atoms within algorithms. Other future directions that Prof. Paolo Carloni from Forschungsz- the cutoff distance are computed using will be explored are the development entrum Jülich, Germany. an exact treatment. Relative timings of models that introduce an additional compared to a fully short-range treat- partitioning, such as QM/QM/MM and ment are shown in the right panel. QM/MM/CG.

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i: Randomi: coil Randomii: coilα-helixii: α-helixiii: β-hairpiniii: β-hairpiniv: Extendediv: Extendedv: Helix-coil-helixv: Helix-coil-helixvi: βvi:-floor/helixβ-floor/helixvii:vii: Helical Helical bundle bundle

Figure 3: Phase diagram for model peptides as a function of the coiling propensity λ, and the hydrophobicity α for different lengths of the peptide.

Coarse-grained/mesoscale density functional-based mean-field. dielectric function ε (Figure 4). resolutions Figure 3 2018 brought significant advances in the development of the hybrid particle/ Molecular dynamics simulations on field (hPF) methodology by the Cascella a series of test systems showed how by functional derivation (passages omit- group at UiO. In early 2018, the first the hPF model is able to capture all ted), we can deduce that a particle of model for peptides was published in the main features of polypeptides. In type K is subject to a potential: the Journal of Chemical Theory and Com- particular, homopolymers of different putation [2]. In this model, the intra- lengths yield a complex folding phase molecular potential for the peptide diagram, extending from the collapsed chain is built on a two-bead coarse to swollen state (Figure 3). Moreover, The first term is the electrostatic poten- grain mapping for each amino . A simulations on models of a four-helix tial energy of the charge, the second one combined potential for the bending and bundle and of an α+β peptide show how is due to the polarization. Consistently torsional degrees of freedom ensures the collapse of the hydrophobic core with the hPF formalism, one can write the stabilization of secondary structure drives the appearance of both folded the dielectric function as dependent elements in the conformational space motifs and the stabilization of tertiary on the local density of the species: of the polypeptide. Finally, the elec- or quaternary assemblies. Finally, the r r X r , where X r) is trostatic associated with the polypeptide model is able to structurally the molarη fractionη η of theη speciesη at ε( )=ε({ϕ ( )})=∑ ( ) ε ( peptide bonds of the main chain are re- respond to the environmental changes position r, and is a value of the die- η constructed by a topological procedure caused by the presence of a lipid bilayer. lectric permittivity formally assigned εη as previously introduced by Cascella et to the same species. al [3]. Unlike the intramolecular terms, During 2018, we also developed a gen- the intermolecular interactions com- eralised formalism for the treatment The electrostatic potential is determined prising both the solute and the explicit of electrostatic interactions in hPF in according to the generalised Poisson solvent are not directly computed by non-homogeneous phases. By defining equation: many-body position-dependent poten- the total electrostatic energy as a func- tials. Instead, they are introduced as a tion of the displacement fieldD and the ∆ ε r)∆ψ r r). ∙[ ( ( )]=–ϱ(

Hylleraas annual report 82 2017 | 2018 RT Activity Reports –

( (r) ∇ ψ(r)) = ∇ ρ( − r) ) r (

Figure 4: Schematic representation of a lipid bilayer, and the corresponding drop in the dielectric function.

We proved that this scheme is able to PI of the collaborative research centre In 2019, at the end of her MSC fellow-­ reproduce the behaviour of ideal ions TRR-146 – Multiscale Simulation Methods ­ship, Dr. H. Bindu Kolli left the Hylleraas partitioning in water/oil mixtures, for Soft-matter Systems with the project: Centre for a new position as research and that it can predict the correct low Multi-scale resolution methods including associate at the University of Sheffield, permeability of both zwitterionic and quantum chemistry, force fields, and hybrid UK. We wish her all the best for a bril- charged membranes to ideal ions [4]. particle-field schemes. This initiative is liant continuation of her career! funded by the Deutsche Forschungs- Current developments involve the defi- gemeinschaft, shared by the Johannes References: nition of a first model for nucleic acids, Gutenberg-University in Mainz, the 1 J. M. H. Olsen, V. Bolnykh, S. Meloni, as well as a rigorous formalism for the Max-Planck Institute for Polymer Re- E. Ippoliti, M. P. Bircher, P. Carloni, and treatment of surfaces and anisotropic search, and the Technical University of U. Rothlisberger, Preprint on ChemRxiv 2019, https://doi.org/10.26434/chemrx- pressure coupling. Darmstadt. The project aims to build a iv.7635986. dynamic platform combining multiple 2 S. L. Bore, G. Milano and M. Cascella, All the hPF developments have been codes for multi-scale simulations with J. Chem. Theory Comput. 2018, 14, possible thanks to the excellent work automatic on-the-fly definition and usage 1120-1130. by PhD student Sigbjørn L. Bore, and of the most appropriate resolution(s). 3 M. Cascella, M. A. Neri, P. Carloni MSC fellow Dr. H. Bindu Kolli. The pro- The project involves two PhD students and M. Dal Peraro, J. Chem. Theory ject involves the crucial collaboration (M. Ledum, located at Hylleraas-UiO, and Comput. 2008, 4, 378-1385. with Prof. G. Milano from Yamagata T. Kirsch, in Mainz), and sees a naturally 4 S. L. Bore, H. B. Kolli, T. Kawakatsu, University, Japan. converging objective with the develop- G. Milano and M. Cascella, J. Chem. Theory Comput. 2019, published ment of the MiMiC framework pursued online. Funding / Personnel at Hylleraas-UiT. In February 2018, Jógvan Magnus Haugaard Olsen was employed as a During the last months of 2018 a new researcher at Hylleraas-UiT, mainly collaboration between the two projects to work on the development­ of multi­ was established. scale models and tools. Since June 2018, Michele Cascella has been appointed

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Spectroscopic Processes

Principal investigators: Kenneth Ruud and Thomas Bondo Pedersen

In RT3, we develop computational Attosecond quantum dynamics with coupled-cluster theory is formally exact tools for describing the experi- time-dependent coupled-cluster (full configuration interaction limit). mental observations that will be theory A new PhD student, Håkon Emil Kris- tiansen, who started in August 2018, is realized at the new light sources. As ever more powerful light sources addressing this fundamental challenge, RT3 builds on the developments emerge, reliable quantum-mechanical simulation methods are urgently needed using a single-particle basis moving in in RT1 and RT2 to also describe to properly plan, execute, and interpret concert with the correlating amplitudes. spectroscopic processes of in- experiments involving ultrashort and Initial computational experiments are creasingly complex systems. highly intense laser pulses. During 2018, highly promising and Kristiansen has – Prof. Thomas Bondo Pedersen and Dr. started to work on his first manuscript Simen Kvaal worked on the stable inte- on this subject. gration of the time-dependent coupled- cluster equations and suggested a novel Relativistic extensions interpretation of the coupled-cluster In parallel to the developments of wave function based on the time- coupled-cluster based time-propagation dependent bivariational principle. In techniques, we have been pursuing a a paper submitted for publication in relativistic extension of this method- December 2018 [1], it has been demon- ology at the density-functional theory strated through computational experi- (DFT) level. This work has been spear- ments that the standard formulation of headed by Dr. Lukas Konecny and Dr. coupled-cluster theory – using a static Michal Repisky. Of particular focus in Hartree-Fock reference determinant 2018 has been the extension of this for- – becomes numerically unstable as in- malism to chiroptical , tense laser pulses pump the electronic electronic circular dichroism and op- system out of the ground state and into tical rotatory dispersion [2], important a superposition of excited states. This is methods for the investigation of chiral even observed in the limit where molecules. Work is ongoing with Prof.

Hylleraas annual report 84 2017 | 2018 15 Se




1c ECD spectrum ECD 5 2c 10 4c

2 4 6 8 10 12 Energy [eV] 20

15 Se 1515 SeTe

10 1010

5 55

0 0 0

5 1c ECD spectrum ECD 1c 1c spectrum ECD 5 ECD spectrum ECD 5 2c2c 2c 10 10 4c 10 4c4c

2 4 6 8 10 12 22 44 66 88 1010 RT Activity1212 Reports Energy [eV] Energy [eV] 20 20 – 15 Se TePo 15 Te 1510 10 10 10 5 5 5 5 0 0 0

1c 55 1c ECD spectrum ECD 5 spectrum ECD 1c 1c spectrum ECD ECD spectrum ECD 2c 2c2c 10 10 4c 10 4c4c

2 4 6 8 10 12 2 2 4 4 6 6 8 8 1010 1212 Energy [eV] Energy [eV] 20 10 15 PoTe PoLv 10 10 10 5 5 5 5 0 0 0 5 5 1c 1c ECD spectrum ECD ECD spectrum ECD 5 1c 5 1c spectrum ECD ECD spectrum ECD 2c 2c2c 10 2c 4c 10 4c 10 4c 10 4c

2 2 4 4 6 6 8 8 1010 12 0 2 2 4 4 6 6 8 8 1010 1212 Energy [eV] Energy [eV]

10 Po 10 Lv 10 Lv

5 5 The5 figure shows the non-relativistic (1c) and relativistic (2c/4c) circular dichroism spectra of C4H8X (X=Se, Te, Po, Lv) illustrating the gradual breakdown of the 0 0 non-relativistic0 approximation.

5 5 5 1c ECD spectrum ECD 1c 1c spectrum ECD ECD spectrum ECD 2c 2c 10 10 4c 4c

0 2 2 4 4 6 6 8 8 1010 12 0 2 4 6 8 10 12 Energy [eV] Energy [eV]

10 Lv Patrick Norman and Dr. Nanna List plementing the complex polarization Relativistic effects and to extend5 these studies to the X-ray propagation at the two- and four-com- molecular stability region: X-ray natural circular dichro- ponent relativistic DFT levels. A par- 0 Together with Prof. Abhik Ghosh, adjunct ism (XNCD). As chiral molecules are ticular target for these developments, professor Jeanet Conradie and Dr. Taye large5 and have only limited symmetry, as well as for the relativistic real-time 1c Demissie, Ruud has investigated why ECD spectrum ECD efforts have2c been made on code opti- time-dependent DFT methods, will there are no ruthenium and osmium 10 4c mization, and we have implemented be open-shell systems as relativistic analogues of nitrosylheme. It was found both 0the X2C2 approximation4 6 8and res10 - 12spin-orbit effects in many cases are that low ionization potentials for the Energy [eV] olution-of-the-identity methods in the more important for open-shell systems heavier analogues of the nitrosylhemes, relativistic program system ReSpect [3] and because such computational tools brought about by relativistic effects, are for these calculations. Extensive tests are currently lacking. the reason for their lack of stability, have been performed to ensure that and thus lack of experimental obser- these approximations do not lead to no- NMR and EPR of heavy-element vation [5]. The study also highlighted ticeable errors in the calculated results. compounds the limitations in current density func- In collaboration with researchers at tionals in that different well-established Frequency domain the national NMR laboratory of the functionals give rise to very different Time propagation is important for the Czech republich in Brno, Ruud have electronic structures for the osmium study of systems in very strong fields studied the electronic spin structure nitrosylhemes. and for very short pulses. For many and metal-ligand bonding in a series experiments, including many of those of square-planar iridium catalysts us- Vibrational spectroscopy that will be routinely performed at the ing relativistic methods [4]. The work Dr. Magnus Ringholm has for several fourth-generation light sources, per- was initiated through the visit of a PhD years been developing a flexible frame- turbation theory will remain a valid student from the Czech group, Pankas work for the calculation of high-order approximation. In these cases, it is Bora, as well as visits by both Ruud response functions. In 2018, he pub- more efficient to perform calculations and Repisky to our Czech collaborators. lished together with US collaborators in the frequency domain. Konecny and a highly accurate study of the equilib- Repisky have been working on im- rium structure and vibrational frequen-

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cies of formaldehyde, which included Focus in this project has so far been References fourth-order vibrational perturbation on establishing reliable methods to ex- 1 T.B. Pedersen and S. Kvaal, ArXiv: theory calculations in which the frame- plore the large conformational space 1812.04393 work developed by Ringholm was used of these molecules while ensuring a 2 L. Konecny, M. Kadek, S. Komorovsky, to obtain sixth-order geometrical deriv- reliable prediction of the chiroptical K. Ruud and M. Repisky, J. Chem. atives of this molecule [6]. In parallel to spectra of these molecules. Phys. 2018, 149, 204104. this work, Ringholm has been working 3 ReSpect 5.0.1 (2018), relativistic spec- troscopy DFT program of authors M. on a general approach for calculating Excited-state properties Repisky, S. Komorovsky, V. G. Malkin, multidimensional vibrational spectra. Dr. Mehboob Alam has together with O. L. Malkina, M. Kaupp, K. Ruud, with This work has in part been put on hold Beerepoot and Ruud worked on un- contributions from R. Bast, R. Di Rem- during 2018 due to the preparation of ravelling the structural features that igio, U. Ekström, M. Kadek, S. Knecht, L. Konecny, E. Malkin, I. Malkin Ondik the first release of OpenRSP [7]. The support large two-photon absorption http://www.respectprogram.org/ general framework for response func- cross sections. In addition to rational- tions of arbitrary order implemented 4 P. L. Bora, J. Novotny, K. Ruud, S. izing the observed structure-property Komorovsky and R. Marek, J. Chem. in OpenRSP was part of the LSDalton relations using channel interference Theory Comput. 2018, 15, 201. release at the end of 2018. models [10,11], they have performed 5 T. B. Demissie, J. Conradie, H. detailed benchmarks of the perfor- Vazquez-Lima, K. Ruud and A. Ghosh, Increasing complexity mance of different exchange-correlation ACS Omega 2018, 3, 10513. PhD student Karen Dundas, supervised functionals for the calculation of 6 W. J. Morgan, D. A. Matthews, M. Ring- by Dr. Jógvan Magnus Haaugard two-photon absorption cross sections holm, J. Agarwal, J. Z. Gong, K. Ruud, Olsen, RIngholm, Ruud and Dr. Maarten against high-level coupled-cluster cal- W. D. Allen, J. F. Stanton and H. F. Schaefer III, J. Chem. Theory Comput. Beerepoot, has been working on ex- culations [12]. 2018, 14, 1333. tending the open-ended framework 7 [OpenRSP] OpenRSP, an open- to include the effects of a solvent or Triplet excited-state properties ended response property library, protein environment, described by a Together with Dr. Swapan Chakrabarti www.openrsp.org polarisable embedding model [8]. She from the University of Kolkata, a visitor 8 J. M. H. Olsen, K. Aidas and J. focuses in particular on the inclusion to the Hylleraas Centre, Ruud has been Kongsted, J. Chem. Theory Comput. 2010, 6, 3721. of these effects for the modelling of engaged in the study of several key pro- vibrational spectroscopies. Following cesses involving triplet excited states, 9 J. M. H. Olsen, C. Steinmann, the initial implementation of regular K. Ruud and J. Kongsted, such as triplet lasers and white-light- J. Phys. Chem. A 2015, 119, 5344. infrared and Raman spectroscopies, emitting diodes. They have demonstrat- the next goals will be the modelling of 10 Md. M. Alam, M. T. P. Beerepoot and ed that accurate modelling is possible K. Ruud, J. Chem. Phys. 2017,146, vibrational chiroptical spectroscopies as when including all possible internal 244116. well as the extension to the polarizable conversion processes as well as inter- 11 Md. M. Alam, R. Misra and K. Ruud, density-embedding approach [9]. system crossings, and have unravelled Phys. Chem. Chem. Phys. 2017, 19, novel insight into the origins of exper- 29461. Chiroptical spectroscopy imental observations of both triplet 12 M. T. P. Beerepoot, Md. M. Alam, of natural products lasers [13] and in organic phosphors J. Bednarska, W. Bartkowiak, K. Ruud and R. Zalesny, J.Chem. Theory The framework developed by Dundas [14]. Ruud has also been involved in Comput. 2018, 14, 3677. will be an important tool for the work studies of emission processes together 13 L. Paul, A. Banerjee, A. Paul, K. Ruud of PhD student Karolina Eikås, who with Russian colleagues [15], and in studies the modelling of vibrational and S. Chakrabarti, J. Phys. Chem. particular Dr. Vladimir Pomogaev from Lett. 2018, 9, 4314. chiroptical properties of large cyclic Tomsk State University, with whom 14 L. Paul, T. Moitra, K. Ruud and S. polypeptides as part of the Digibiotics he shares a joint Russian-Norwegian Chakrabarti. J. Chem. Phys. Lett., project lead by Prof. John-Sigurd Svend- collaborative project. 2019, 10, 369. sen. The ultimate goal of this project is 15 V. A. Pomogaev, R. R. Ramazalov, the identification of new natural com- K. Ruud and V. Ya. Artyukhov, J. pounds with antimicrobial activity. Photochem. Photobiol. 2018, 354, 86.

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Extreme Environments In RT4, we explore the exotic, squeezed chemistry of ultra- strong magnetic fields and high pressure. In 2018, we have studied the ionization of atoms and the stability of larger molecules in ultrastrong magnetic fields, closed-shell para­ Principal investigators: magnetism, density-functional theory in the presence of a Trygve Helgaker and magnetic field, and the melting of rare under high Kenneth Ruud pressure in the presence of a magnetic field. Many of the projects were in collaboration with fellows at the Centre for Advanced Study (CAS) during 2017–2018. –

Stability of molecules in strong B0 = 235kT. We have found that these the states is observed as illustrated for magnetic fields molecules are stable although the bind- the and molecule 2 A fundamental and important question ing mechanisms may be different in the in Figure. At zero field, the P state of regarding molecules in a magnetic field presence of a magnetic field than in the flourine (with one unpaired electron) is is their stability. Does a molecule that absence of it. Particularly surprising is the ground state. Conversely, at a field exists under the prevalent conditions the existence of a new chemical bond- strength of about one atomic unit, the 4 of Earth, where magnetic fields are ing mechanism, paramagnetic bonding, F state with three unpaired electrons weak, exist on magnetic white dwarfs, which comes into play at field strengths is the ground state, while the original where the magnetic fields are orders of about 100 kT. ground state has become a highly excited of magnitude stronger? We have pre- state. In Figure 2, we have also plotted viously studied small molecules con- The question of molecular stability in the energies of the lowest electronic sisting of hydrogen and helium atoms strong fields is made complicated by the states of benzene (C6H6) as functions of in strong magnetic fields, on the order fact that the ordering of the electronic the magnetic field strength. While the of one atomic unit field strength, states is strongly affected by magnetic ground state of the benzene molecule is fields—in fact, a complete reordering of a closed shell at zero field, it has eight

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Figure 1: The energy of the lowest states of the fluorine Figure 2: The energy of the lowest states with 0, 2, 4, 6, and 8 atom as a function of the magnetic field strength (atomic unpaired electrons as a function of the magnetic field strength units). [S. Stopkowicz et al., J. Chem. Phys. 2015, 143, (atomic units) 074110]

unpaired electrons at one atomic unit Paramagnetic bonding thus appears electron can have zero energy in the field strength. to be a general bonding mechanism in absence of a magnetic field, the lowest Figure 1 and 2 strong fields – and eventually dominant energy in the presence of the field is in the regime where all electrons have the energy of the lowest Landau level In general, electronic states with many beta spin. Figure 3 (next page) consistent with the spin and orbital unpaired electrons are less stable than angular momentum of the electron [2]. molecules with only paired electrons, Ionization energies in suggesting that a molecule becomes a magnetic field Closed-shell more unstable as more and more elec- The quantum-mechanical calculation When a magnetic field is turned on, the tron pairs are uncoupled by the field. of ionization energies is routine for energy of a molecule either decreases On the other hand, we have learned systems in the absence of a magnetic (paramagnetism) or increases (dia- field. Their calculation in the presence from studies of H2 that the unpaired magnetism). Paramagnetism occurs triplet state (with two beta electrons) of magnetic field requires the develop- when the molecule has a permanent is stabilized by paramagnetic bonding, ment of new electronic structure soft- magnetic moment. In the absence of a indicating that the unpaired high-spin ware. At the Centre for Advanced Study magnetic moment, the energy increases states can be bound paramagnetically. (CAS), the first code for the calculation diamagnetically as a result of induced of ionization potentials for molecules precession of the electrons about the To study bonding in larger molecules, in magnetic field was developed [2]. field direction. Initial studies of atoms in magnetic field we chose the molecule CH4 [1].

As the field is turned on, the tetrahedral of strength up to 0.25B0 have shown However, there are a few notable ex- methane molecule becomes twisted and that the ionization energies increase ceptions to this rule. Some closed-shell eventually becomes planar in a per- in near-linear manner with increasing molecules such as BH and CH+ are par- pendicular orientation relative to the field strength, with a slight concavity. It amagnetic, even though they have no field. Moreover, each is an interesting observation that most permanent magnetic moment in the remains attached to the central carbon of this stabilization is caused by the in- absence of a magnetic field. We have atom by paramagnetic bonding with creased energy of the emitted electron performed highly accurate studies of two unpaired electrons; see Figure 3. in the magnetic field — while an emitted these molecules and demonstrated how

Hylleraas annual report 88 2017 | 2018 RT Activity Reports –

Figure 3: Structure and relative energies of CH4 and its

fragments in a magnetic field of strength 0.9B0 [1]. All CH bonds are paramagnetic rather than covalent.

their paramagnetism arises as a result Density-functional theory we have proposed a simplified meth- of a complicated interplay of the ground in magnetic fields od: linear vector potential-DFT (LDFT), state with low-lying excited states in The most frequently used method for developed for the important special the presence of a magnetic field [3]. quantum-chemical studies of mol- case of vector potentials that depend Figure 4 (next page) ecules is density-functional theory linearly on the magnetic field vector [6]. (DFT), which strikes a good balance Unlike in conventional current-density In Figure 4, we have plotted the energies between quality and cost. In our group, functional-theory (CDFT), the density of the four lowest electronic states of we have over the last few years worked functional in LDFT does not depend BH against the field strength for parallel on the generalization of this method to on the paramagnetic current at each and perpendicular orientations of the molecules in magnetic fields since it is point in space but only on six variables molecule. In the parallel orientation, needed for the study of large systems – namely, the canonical momentum the ground state (blue) is diamagnetic; in a magnetic field [4,5]. In the most re- and the paramagnetic contribution to the remaining states are paramagnetic cent work [5], we analyse the different the magnetic moment of the electronic and we observe a number of level cross- components to the Kohn–Sham DFT system. ings. In the non-parallel orientations, energy in a magnetic field for dia- and all states are of the same symmetry and paramagnetic molecules. The challenge Confined electronic systems the crossings are avoided. As a result of is to incorporate the dependence on A common feature of electronic systems such an avoided crossing, the closed- the magnetic field into the exchange– under high pressure and in a strong shell ground states bends down already correlation functional in a physically magnetic field is confinement – that at zero field, resulting in closed-shell meaningful and useful manner. We is, the squeezing of the systems into a paramagnetism. Thus, closed-shell have identified the meta functionals, region of space smaller than they nor- paramagnetism occurs as a result of a which contain a dependence on the mally occupy. We have studied confine- complicated interplay of the closed-shell kinetic energy density, as a useful level ment in an idealized sense, introducing ground state with open-shell excited of theory for DFT in magnetic fields. a confinement potential whose steep- states. This work was presented in a ness can be adjusted parametrically plenary lecture at the ICQC congress As an alternative to established versions [7]. Of particular interest to us is the in Menton 2018. of DFT for molecules in magnetic field, strong connection between confinement

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Figure 4: The lowest states of BH as a function of the magnetic field strength for parallel (left) and perpendicular (right) field orientations (atomic units). [3]

and diamagnetism. It is well-known the melting of rare gases under high maximum of the heat capacity) increas- that magnetic fields favour states of pressure in the presence of a strong es with increasing field strength. This high-angular momentum (see Figure 1) magnetic field [9]. We simulated phase melting-point increase, which has never but the explanation for this has always transitions by exploring phase space before been observed, can be ration- been in terms of the paramagnetic part with classical (parallel-tempering) Mon- alized in terms of the stabilization of of the Hamiltonian. It was an eureka te-Carlo methods combined with a very electronic systems by a magnetic field. moment for us to understand that also accurate computation of the interaction After an initial quadratic region, the the diamagnetic part of the Hamiltonian energy of the sampled configurations, melting temperature increases linearly favours high angular momentum. It fol- employing many-body expansions in with increasing field strength by about lows that an applied magnetic field – for which the total interaction energy of an 0.15 mK/T. all systems and under all conditions – N-atom system is obtained by decom- stabilizes electronic states of high (spin posing the total energy into two-, three- We are currently exploring the melt- or orbital) angular momentum. and higher-body fragments. For the ing of extended systems under high two- and three-body contributions, we magnetic fields by using the results for On a related topic, in a collaboration used the highest level of quantum-me- small clusters and extrapolating to the with Ludwik Adamowicz, a frequent chanical treatment possible. This work infinite system in a manner that has visitor to the Hylleraas Centre from the was initiated at CAS and depends heav- previously been successfully applied University of Arizona, we have studied ily on the experience and expertise of to describe melting in the absence of the HD molecule trapped in a cavity Elke Pahl and Peter Schwerdtfeger on a magnetic field. created by a fast-rotating strong mag- rare- melting. netic field [8]. The electronic system is Figure 5 Meetings and workshops described using explicitly correlated The meeting Atoms, Molecules and Mate- Gaussians (ECGs) in a non-Born–Oppen­ Our first results are for neon clusters of rials in Extreme Environments, Norwegian heimer manner. different sizes in strong homogeneous Academy of Science and Letters (June

magnetic fields up to 0.3B0. In Figure 5, 15–17 2018) was organized by RT leader Melting in strong magnetic fields we have plotted the heat capacity of Trygve Helgaker, who also was co-

In a study that combined pressure Ne55 as a function of the temperature, organizer of the workshop Mathe- with a magnetic field, we considered illustrating how the melting point (the matical Methods in Quantum Chemistry,

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Heat Capacity for Ne 55 9 B=0.00 au B=0.05 au 8 B=0.10 au B=0.15 au 7 B=0.20 au B=0.25 au 6 B=0.30 au / K ] l 5

4 [ k J / m o

v 3 C



0 5 6 7 8 9 10 11 12 13 14 15 16 Temperature [K]

Figure 5: The heat capacity at constant volume for Ne55 plotted against the temperature at various magnetic field strengths.

Mathematisches Forschungsinstitut year 2017–2018. In addition, frequent 4 S. Reimann, A. Borgoo, E. I. Tellgren, Oberwolfach, Germany (March 18–24 visitor Prof. Ludwik Adamowicz, Uni- A. M. Teale, and T. Helgaker, J. Chem. 2018). A mini-symposium Frontiers in versity of Arizona, Tucson collaborates Theory Comput. 2017, 13, 4089–4100. Density-Functional Theory was held at on molecules in a strong magnetic field 5 S. Reimann, A. Borgoo, J. Austad, E. I. Tellgren, A. M. Teale, T. Helgaker, the Hylleraas Centre in Oslo (Novem- beyond the Born–Oppenheimer approx- and S. Stopkowicz, Mol. Phys. 2019, ber 1 2018). imation, whereas astrophysicist Dr. 117, 97–109. Anand Thirumalai, DigiPen Institute 6 E. Tellgren, A. Laestadius, T. Helgaker, Funding of Technology, Redmond, Washington S. Kvaal, and A. M. Teale, J. Chem. Prof. Trygve Helgaker won a FRINATEK and Prof. Jeremy S. Heyl, University of Phys. 2018, 148, 024101. grant Magnetic chemistry from the Re- British Columbia, Vancouver collaborate 7 L. F. Pasteka, T. Helgaker, T. Saue, D. search Council of Norway for the peri- on aspects of the work of astrophysical Sundholm, H.-J. Werner, M. Hasanbulli, relevance. J. Major, and P. Schwerdtfeger, Atoms and od 2019-2022, for a total of 11 MNOK, molecules in soft confinement potentials, allowing him to hire two postdocs and in preparation. References one Ph.D. student. 8 L. Adamowicz, M. Stanke, E. Tellgren, 1 M. Dimitrova, D. Sundholm, and T. Helgaker, J. Chem. Phys. 2018, Personell T. Saue, S. Stopkowicz, and 149, 244112. T. Helgaker, Halomethanes in Apart from leader T. Helgaker and co-leader a strong magnetic field, 9 J. Wiebke, O. Smits, P. Jarebek, K. Ruud, the personnel on RT4 are Adj. in preparation. P. Schwerdtfeger, E. Florez, S. Stopkowicz, A. M. Teale, W. Klopper, Prof. Andrew Teale, Dr. Alex Borgoo, Dr. 2 C. Holzer, A. M. Teale, F. Hampe, T. Helgaker, and E. Pahl, Melting in a Erik Tellgren, Dr. Sangita Sen and Ph.D. S. Stopkowicz, T. Helgaker, and strong magnetic field, in preparation. student Sarah Reimann. Borgoo and W. Klopper, J. Chem. Phys. 2019, 150, 214112. Reimann left the Hylleraas Centre 3 S. Stopkowicz, F. Hampe, J. Gauss, in the course of 2018. More person- W. Klopper, A. M. Teale, A. Borgoo, will will be hired on the grant Magnetic E. Tellgren, and T. Helgaker, Chemistry and also on internal funding. Closed-shell molecular Many of the fellows of the CAS project paramagnetism, in preparation. Molecules in Extreme Environments con- tributed to RT4 during the academic

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Chemical Transformations

Principal investigators: Odile Eisenstein and Kathrin Hopmann

The RT5 research team has in 2018 Scientific focus Non-precious metals focused on important transition The research in RT5 has focused on the We have had particular focus on metal-catalyzed reactions, ex- computational modelling of transition non-precious metals and have reported plaining their behavior, activi- metal complexes, both their proper- that iron-catalysts provide easy access ty, and selectivity. The team has ties and their reactions. The studied to various heterocycles, based on the published 17 research articles and transformations are from important experimental work by postdoc Jana- areas such as hydrogenation and de- kiram Vaitla and the computational presented their work at 10 inter- hydrogenation, carboxylations, het- work by Hopmann [1a] (see associated national conferences. erocycle formation, water oxidation, research highlight). A collaboration of – activation of small molecules and the David Balcells with the Pérez group development of molecular organic (CIQSO, Spain) on Cu-catalyzed dehy- frameworks (MOFs) for the reduction drogenation reactions was extended of and the oxidation towards the hydroxylation of aromatic of methane. One of the fundamental compounds [1b]. In this work, the com- activities of RT5 is the collaboration bination of DFT calculations with mech- with local experimental groups, which anistic experiments revealed two com- involves both the peting pathways, in which electrophilic group at UiT and the Catalysis Group substitution prevailed over rebound. at UiO. These projects pursue the inter- The conclusions were supported by disciplinary collaboration between experimental Hammett correlations. We different fields, including the use of have further shown that cobalt-based computational modelling in catalysis hydrogenation catalysts have access to and materials science. Beyond the joint different reaction pathways (with and publications, the collaboration is hav- without chemistry), depending on ing a positive impact on the training of the type of substrate (in collaboration the PhD students, which gain insight with Prof. Chirik, Princeton University), and expertise in both experimental and with the main work performed by RT5 computational chemistry. postdoc Glenn Morello, under supervi-

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Figure 1: Left: Computational mechanisms require validation. Right: Unusual transition state for C-CO2 bond formation

sion of Hopmann [1c]. In this work, we for the injection of excited electrons into Computational NMR as a tool emphasized the need of computational the linker-SBU scaffold of the MOF. Eirik In the study of the properties of tran- chemists to validate their proposed Thoresen, who obtained his PhD degree sition metals, we have had focus on mechanisms appropriately. in November 2018, did this work under Nuclear Magnetic (NMR), Figure 1 the supervision of Balcells (computa- a versatile tool for characterization of tional) and Profs. Tilset and Amedj­kouh chemical systems. Our impetus for this (experimental, UiO). To explore the work originated from experimental data direct incorporation of CO into other CO2 as a resource 2 obtained by collaborator Christophe molecules, PhD students Marc Obst and In our efforts to employ CO as a re- Copéret at ETH Zurich. NMR solid-state 2 Ljiljana Pavlovic, together with the main placement of fossil-based carbon, we measurements, carried out to charac- supervisor Hopmann, have compiled are interested in the development of terize species involved in π-bond me- a review on computational studies of nanoporous catalytic materials based tathesis, showed unusual variations known C-CO bond formation reactions on MOFs. The goal is to exploit the high 2 of the shielding tensors at the metal [1e] and Ljiljana and Janakiram have absorption capacity of these systems to bound carbon atom. Two-component further studied rhodium-catalyzed hy- promote the photocatalytic reduction ZORA calculations of the shielding ten- drocarboxylation, both computationally of CO . We developed a series of cyclo- sors at the investigated carbon atom 2 and experimentally, under supervision metallated Ru complexes containing reproduced the experimental data with of Hopmann and collaborator Assoc. carboxylic substituents in their biaryl good accuracy. More interestingly, a Prof. Bayer (UiT) [1f]. Based on our [1d]. These functional groups Natural Chemical Shift (NCS) analysis work, we propose that CO in many were added into the UiO-67 MOF. 2 provided the contributions of bonds and cases may form C-C bonds without in- The nature of the UV-Vis electronic lone pairs to the shielding tensor at the teracting with the metal; this implies transitions, which play a key role in studied atom, establishing a link with that reaction additives may be useful photocatalysis, was rationalized in a the reactivity at this atom. In 2018, we to bind and activate CO . Currently the time-dependent DFT (TD-DFT) study. 2 focused on the alkyl RT5 team is studying relevant additives The calculations showed that the most complexes with formal M-C single computationally and experimentally, in intense excitations involved π*-acceptor bonds having unusually high chemi- collaboration with Bayer and Hylleraas orbitals with a strong contribution from cal shift and large tensor anisotropy. PI Michele Cascella (RT2). the carboxylic groups, showing promise The calculations indicated that these

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Ljiljana Pavlovic and Marc Obst (in the photo) joined Ainara Nova and Kathrin Hopmann at the conference in Tarragona in June 2018.

characteristics were due to a partial Au(III) catalysts was based on the use N,O-chelating ligands [4b]. DFT cal- πM-C bond, which itself accounted for of the mppy (methyl-phenyl-pyridine) culations on the electronic structure the observed reactivity. The NMR in- ligand, which has low robustness, and redox potentials of these species formation thus signals the activity of caused by the protonolysis of the showed that the oxidation of their metal-alkyl complexes in H-transfer Au–C bond. This issue was tackled by Ir(IV) precursors is metal-centered. [2a], and olefin polymerization [2b] replacing the methyl of the ligand by Similar properties were observed in reactions. two tert-butyl substituents [3b]. This oxo-bridged Ir(V) dimers, for which new ligand undergoes intramolecular TD-DFT calculations showed that the catalysis C–H activation, yielding an N,C,C gold intense blue colour often observed in Following our previous work on the chelate which is more resistant to prot- Ir-catalyzed water oxidation originated characterization of the first gold(III)-ole- onolysis. Calculations revealed the C-H from electron excitations with a mixed fin complex and the functionalization of activation mechanism, which followed d–d/LMCT character [4c]. and alkynes, we reported the an electrophilic-substitution pathway, characterization of stable Au(III) PNP and disclosed the catalytic mechanism Other projects pincer complexes [3a]. Time-dependent involved in the trifluoro-acetylation of Under our supervision, Jakob Wåh- (TD) DFT was used to understand the acetylene. lander (PhD degree September 2018) intense color of the complexes, which worked on the development of a new is associated with the HOMO–LUMO Water oxidation series of organocatalysts based on chiral transition. Mechanistic calculations The joint work with the group of Prof. phosphoramides, in collaboration with accounted for the low reactivity of Crabtree (Yale University, USA) fostered Prof. Amedjkouh (UiO). In the chiral these complexes towards insertion. a collaboration with RT1 (Hylleraas PI systems, weak interactions induced Javier Grajeda (an exchange student Pedersen) and the Reiher group (ETH moderate to high enantioselectivity from the Miller group, Yale Univer- Zürich) [4a]. This research line contin- [5a]. Nova contributed to the supervi- sity in USA) did this work, under the ued with the study of highly oxidized sion of a PhD exchange student from supervision of Nova and Balcells and Ir complexes related to the catalytic the Hazari group at Yale University, our collaborators Prof. Tilset and Dr. oxidation of water, including the first Patrick Melvin, on bulky Pd catalysts Heyn. Most of our previous work on known Ir(V) complexes supported by for the Suzuki-Miyaura cross-coupling

Hylleraas annual report 94 2017 | 2018 RT Activity Reports –

Figure 2: Spin densities in the anti-ferromagnetic (left) and ferromagnetic (right) states of a Mn-doped cubane oxide. The orange and green isosurfaces represent the alpha and beta spin densities, respectively.

reaction [5b] (see associated research and Javier Grajeda, from University of ber 21–26), RCTF Conference, Toulouse, highlight). Following a 3-month visit North Carolina at Chapel Hill). Nova France (Oct.), the Annual meeting of the at UC Berkeley, Balcells established a and Balcells were visiting research- CO2 Activation Centre, Århus Denmark collaboration with Prof. Tilley on the ers at the ICIQ (Tarragona, Spain) for (November 19–20). Furthermore the study of cubane complexes with a Co4O4 a period of one month. The local RT5 chair of the 16th ICQC organized in metal core. These are used as models of students have also been travelling Menton (June 18–23) is a member the artificial materials and of photosystem abroad, with Marc Obst visiting Prof. RT5 team (see associated report). II. Experimental SQUID measurements Feliu Maseras in Spain for two months. and DFT calculations were combined to Ljiljana Pavlovic visiting Prof. Timo Outlook understand the electronic structure of Repo in Finland for two weeks, and Our work in 2018 has focused on a unique cubane (Figure 2), formed by Lluís Artús visiting Prof. Martin Jaraiz state-of-the-art DFT methods, but introducing manganese as dopant [5c]. in Spain for two weeks. The RT5 team we are in progress to apply various has presented their work at various methods aimed at improving current People, mobility and meetings conferences, among these Bürgenstock, computational protocols for comput- In 2018, the RT5 team hired PhD student Brunnen, Switzerland (April 29 – May ing transition-metal based reactivity. Julie Heron (funded by the Hylleraas 3), Computational Catalysis for Sustaina- This involves i) the artificial force-in- Centre), postdoc Diego García López ble Chemistry, Tarragona, Spain (June duced analysis of reaction pathways (funded by the Tromsø Research 13-15, Figure 2), Dalton Division Cente- (program AFIR [6a], which is applied nary Lecture Award, Warwick, UK, Quan- Foundation) and researcher Torstein to CO2-incorporation reactions, in col- Fjermestad (funded by NordForsk). tum Bio-Inorganic Chemistry IV Bath UK laboration with Prof. Feliu Maseras at We had several visitors: Prof. Agustí (September 3–6), the GEQO Conference, ICIQ), ii) quantum molecular dynam- Lledós from the Autononous Univer- Zaragoza, Spain (September), the ACS ics allowing us to explicitly model the sity of Barcelona, Spain, Louise Pou- Forum: Celebrating Diversity in Inorganic/ solvent and the behavior of additives tot, an exchange student from France Organic Chemistry in Europe, Heidelberg, in solution, for example to understand (Universite de Franche-Comte), and Germany, (October 9–11), the National why cationic or anionic additives used two exchange students from the USA meeting of the Norwegian Chemical Society, experimentally increase so much the (Patrick Melvin, from Yale University, Lillestrøm Oslo (October 16–18), Frontier reaction rates of the Grignard reaction in Chemistry, Yerevan, Armenia (Octo-

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(using the CP2K program, in collabora- References: 4 a) S. B. Sinha, D. Y. Shopov, L. S. tion with Hylleraas PI Michele Cascella), 1 a) J. Vaitla, A. Bayer, K. H. Hopmann Sharninghausen, C. J. Stein, B. Q. iii) automatized modelling of enanti- Angew. Chem. 2018, 57, 16180, b) L. Mercado, D. Balcells, T. B. Pedersen, M. Reiher, G. W. Brudvig and R. H. oselectivity with the program AARON Vilella, A. Conde, D. Balcells, M. M. Díaz-Requejo, A. Lledós , P. J. Pérez, Crabtree, J. Am. Chem. Soc., 2017, [6b], applied to hydrocarboxylation and Chem. Sci., 2017, 8, 8373, c) G. R. 139, 9672. b) L. S. Sharninghausen, S. hydrogenation reactions, and iv) a novel Morello, H. Zhong, H., P. Chirik, K. H. B. Sinha, D. Y. Shopov, B. Q. Mercado, Hylleraas-developed approach that is Hopmann, Chem. Sci 2018, 9, 4977, D. Balcells, G. W. Brudvig ,R. H. Crab- able to eliminate basis set-related errors d) E. M. Thoresen, D. Balcells, S. tree, Angew. Chem., Int. Ed., 2017, 56, 13047, c) D. Y. Shopov, L. S. Sharning- (using the program MRChem, in collab- Øien-Ødegaard, K. T. Hylland, M. Tilset and M. Amedjkouh, Dalton Trans., hausen, S. B. Sinha, B. Q. Mercado, D. oration with Hylleraas PI Luca Frediani), 2018, 47, 2589, e) M. Obst, Lj. Pav- Balcells, G. W. Brudvig, R. H. Crabtree, applied to dissociation and association lovic, K. H. Hopmann, J. Organomet. Inorg. Chem., 2018, 57, 5684. reactions, where such an error plays a Chem. 2018, 864, 115, f) Lj. Pavlovic, 5 a) J. Wåhlander, M. Amedjkouh and D. large role, v) microkinetic models for J. Vaitla, A. Bayer, A. K. H. Hopmann Balcells, Eur. J. Org. Chem., 2019, 442, the interpretation of complex reaction Organometallics 2018, 37, 941. b) P. R. Melvin, A. Nova, D. Balcells, N. Hazari, Mats Tilset, Organometallics, mechanisms in catalysis, vi) machine 2 C.P . Gordon, K. Yamamoto, K. 2017, 36, 3664, c) A. I. Nguyen, L. E. learning with deep neural networks for Searles, S. Shirase, R. A. Andersen, O. Eisenstein, C. Copéret Chem. Sci. Darago, D. Balcells, T. D. Tilley, J. Am. the exploration and understanding of 2018, 9, 1912, b) C. P. Gordon, S. Chem. Soc., 2018, 140, 9030. large chemical spaces, vii) open data Shirase, K. Yamamoto, R. A. Andersen, 6 a) S. Maeda, Y.Harabuchi,, M. Takagi, repositories (ioChem-BD), viii) Correla- O. Eisenstein, C. Copéret, Proc. Nat. T. Taketsugu, K. Morokuma, Chem. tion of NMR parameters with chemical Acad. Sci. USA 2018, 115, E5867. Rec. 2016, 2232, b) Y. Guan, properties. 3 a) J. Grajeda, A. Nova, D. Balcells, Q. V. M. Ingman, B. J. Rooks, and J. Bruch, D. S. Wragg, R. H. Heyn, A. J. S. E. Wheeler. J. Chem. Theory M. Miller, M. Tilset, Eur. J. Inorg. Chem., Comput. 2018, 14, 5249. 2018, 3113, b) M. S. M. Holmsen, A. Nova, K. Hylland, D. S. Wragg, S. Øien-Ødegaard, R. H. Heyn, M. Tilset, Chem. Comm., 2018, 54, 11104.

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Multiphase Systems

Principal investigators: Bjørn Olav Brandsdal and Michele Cascella

The RT 6 team uses computer membrane and/or have intracellular al tools that allow us to probe the water simulations to address impor- targets. As a first step to increase our content surrounding the antimicrobial tant question in chemistry, bi- understanding of their mode of action, agent within the membrane phase, and more sophisticated models of biological preliminary data analysis shows that ology and physics and has in membranes are being developed. solvent molecules are present deep in- 2018 focused on antimicrobial side the membrane. resistance, temperature depend- A PhD student (Laura Liikanen) started Figure 1, next page ence of chemical rates, charged in January 2018 working on construct- soft-matter system and protein ing these membrane models using a Temperature dependence nanocarriers. small library of antimicrobial agents. of catalytic rates Models of gram negative bacteria (E.Co- – 2018 also marked the start of the Topp­ li) with correct lipid composition have forsk project Evolutionary principles of been examined using molecular dynam- biocatalysts from extreme environments Anitmicrobial resistance ics simulations with two membrane with three hirings, senior researcher active compounds. The majority of Driven by the emergence of antibiotic Geir Villy Isaksen, Prof. Johan Åqvist membrane active compounds discov- resistance throughout the world and from Uppsala University as professor ered so far contain 2-5 positive charges, the lack of new antimicrobials in the II (20 %) and Dr. Bjarte Aarmo Lund as and the library used here contains small drug development pipeline, we are on a post doctoral fellow. A fundamental cationic compounds with known activ- the edge of returning to a pre-antibiotic question that remains unanswered is ity. The MD simulations show that the age. To meet this challenge, we are to- what structural modifications are re- active compounds are rapidly inserted gether with researchers in DigiBiotics quired for enzymes to maintain high into the membrane (Figure 1), but ex- exploring new compounds inspired by catalytic activity at temperatures close actly how the “bacterial killing” takes marine Arctic natural products and var- to the freezing point of water. Based place needs to be addressed in more iants thereof. Of particular importance on our earlier computations, increased detail to unravel their mode of action. are middle-spaced molecules with new mobility of surface regions well outside A major question is how the solvation modes of action to reduce the risk of the active site can tune the activation of the charges in the membrane takes emerging resistance. These compounds enthalpy and entropy balance to make can be active against the bacterial place. We have developed computation-

Hylleraas annual report 2017 | 2018 97 RT Activity Reports –

Figure 1: Molecular dynamics snapshots of amphiphatic barbiturates attaching to models of gram-negative bacterial membrane (E.coli).

the reactions less sensitive to temper- to be able to disentangle mutations that also in peptides and peptide/membrane ature. Here, the activation enthalpy affect catalytic activity from those that mixtures. is without exception reduced for all tune the protein stability. Figure 2, next page known enzymes adapted to cold when compared with their warm-active coun- Self-aggregation of charged Formation of protein nanocages surfactants terparts, which seems to be the remedy In 2018, PhD student Raphael M. Pelt- for maintaining a functional metabolism At Hylleraas-UiO, the research in mul- zer, in collaboration with Dr. H. B. Kolli, at low temperatures. We are currently ti-phase systems has concentrated produced a Monte Carlo investigation working with more than ten different on charged soft-matter systems and on the aggregation thermodynamics of cold- and warm-active enzymes to ad- protein nanocarriers. Thanks to the α-tocopherol transfer protein (α-TTP) dress this issue, using both experiments methodological developments of hPF [2]. In a former study [3], Cascella and and computer simulations. with electrostatics, it has been possible co-workers demonstrated how α-TTP, to investigate the aggregation kinetics which in its cellular monomeric state is Construction of computational Arrhe- and thermodynamics of charged sur- responsible for α-tocopherol selection, nius plots require specialized software factants [1]. This research has already can form nano-cages that acquire out- due to the large number of simulations been described in the highlight “The standing transfection properties in cel- needed to obtain sufficient accuracy and effect of concentration on the morphology lular models of the endothelium. Even for data analysis. We have made sig- of charged surfactant assemblies in water” though the structural characterization nificant updates of our software Qgui, and will not be repeated here in detail. of such an aggregate was possible by which will be released early 2019. Of both cryo-EM and x-ray crystallogra- particular relevance to the question of Most importantly, the study in Ref. [1] phy, the (thermo)dynamic features of cold-adaptation is the ability to predict stimulated the definition of a collabora- the self-assembly process remained the effect of point mutations on both tion with Prof. Reidar Lund (UiO), dur- elusive. Thanks to the study by Peltzer, catalytic activity and thermal stability. ing 2018 elected as an affiliated member it was possible to determine that the ag- The latter has now been implemented to the Hylleraas Centre, to investigate gregation proceeds by first trimerization and tested in Qgui using free energy similar aggregation phenomena in more of α-TTP, and then by progressive bind- perturbation protocols. The goal is here complex surfactants, and in the future ing of multiple trimeric units. Structural

Hylleraas annual report 98 2017 | 2018 RT Activity Reports –

Figure 2: Schematics of the self-assembling process of α-TTP.

and bioinformatics data suggest that Funding / personnel The work on soft-matter aggregation this trimer may be indeed the minimal Laura Liikanen will continue the work will be carried out in the next years by transfecting unit. The investigation by on biological membranes and antimi- the newly-appointed PhD student Peltzer was able to propose possible crobial resistance, and a post doctoral Victoria A. Bjørnestad, who is being mutations that would stabilize further position will be announced in 2019. Both co-supervised by Profs. Lund and Cascella. the trimer, thus allowing its structural of these are financed through the Di- and functional characterization. The giBiotics project. In addition, researcher References work was conducted in collaboration Jógvan Magnus Haugaard Olsen will 1 H. B. Kolli, A. De Nicola, S. L. Bore, K. with Prof. A. Stocker, at the University contribute with new methods developed Schäfer, G. Diezemann, J. Gauss, T. Kawakasu, Z.-Y. Lu, Y.-L. Zhu, G. Milano of Bern, Switzerland. in RT2 on problems related to mem- and M. Cascella, J. Chem. Theory Com- brane interactions. Outreach put. 2018, 14, 4928-4937. 2 R. M. Peltzer, H. B. Kolli, A. Stocker and We contributed to the Kjemikonferansen The work on temperature dependence M. Cascella, J. Phys. Chem. B 2018, March 15–16, 2018, which gathered about of rates will be con- 122, 7066-7072. 200 high school students and teachers tinued for the next years by senior re- 3 W. Aeschimann, S. Staats, S. Kam- from Nordland, Troms and Finmark, searcher Geir Villy Isaksen, post doc- mer, N. Olieric, J.-M. Jeckelmann, D. with a four hour session devoted to toral fellow Bjarte Aarmo Lund, Prof. Fotiadis, T. Netscher, G. Rimbach, M. Cascella and A. Stocker, Sci. Rep. antimicrobial resistance. The students Johan Åqvist and supplemented by two 2017, 7, 4970. were given hands-on practical exercises Phd students and a 3-year post doctoral where the proteolytic stability of an- fellow to be hired in the spring 2019. timicrobial compounds was examined These positions are all financed through using computational docking and scor- the Toppforsk grant Prof. Brandsdal ing methods. received in 2018.

Hylleraas annual report 2017 | 2018 99

Hylleraas members –

Leadership and Principal Investigators –

Trygve Helgaker Kennesath Ruud Director Deputy Director Professor Professor UiO UiT

Thomas Bondo Pedersen Michele Cascella PI Professor PI Professor UiO UiO

Odile Eisenstein Bjørn Olav Brandsdal PI Professor PI Professor UiO UiT

Kathrin Hopmann Luca Frediani PI Assoc. Professor PI Assoc. Professor UiT UiT

Hylleraas annual report 100 2017 | 2018

Researchers –

Simen Bin Gao Heike Kvaal UiT Fliegl UiO UiO

Ainara Alex Erik Nova Borgoo Tellgren UiO UiO UiO

Peter David Torstein Wind Balcells Fjermestad UiT UiO UiO

Stig Rune Geir Jogvan Jensen Isaksen Magnus UiT UiT Haugaard Olsen UiT

Geir Arnfinn Maarten Isaaksen Hykkerud Beerepoot UIT Steindal UiT UiT

Thomas Sangita Håbu Sen Qureishy UiO UiO

Hylleraas annual report 2017 | 2018 101

Hylleraas members –

Postdocs –

Hima Gustav Kacper Bindu Kolli Baardsen Blaziak UiO UiO UiO

Rolf Andre Glenn Heilemann Laestadius Morello Myhre UiO UiT UiO

Mehboob Diego Lukas Alam García- Konecny UiT López UiT UiT

PhD Students –

Julie Morten Håkon Emil Héron Ledum Kristiansen UiO UiO UiO

Karen Oda Lluis Artus Jon Hjorth Suarez Austad Dundas UiO UiO UiT

Hylleraas annual report 102 2017 | 2018

PhD Students –

Sarah Chandan Raphael Reimann Kumar Mathias UiO UiO Peltzer UiO

Marius Tor Arne Sigbjørn Kadek Andberg Løland Bore UiT UiT UiO

Audun Skau Ljiljana Birta Hansen Pavlovic Ravdna UiO UiT Sarre UiT

Benedicte Fabian Joakim Ofstad Maximilian Samuel UiO Faulstich Jestilä UiO UiO

Anders Marc Magnar Myhre Obst Bjørgve Brakestad UiT UiT UiT

Karolina Laura Marc Solheimslid Liikanen Joosten Eikås UiT UiT UiT

Hylleraas annual report 2017 | 2018 103

Hylleraas members –

Affiliates –

Einar Mats Reidar Uggerud Tilset Lund Professor Professor Assoc. UiO UiO Professor UiO

Ute Tor Flå Knut Krengel Professor Fægri Professor UiT Professor UiO Emertius UiO

Inge Røeggen Professor Emeritus UiO

Overseas Research Grant Holders Administration – –

Roberto Magnus Jan Ingar Di Remigio Ringholm Johnsen USA Sweden Head of Office UiT UiT

Stig Eide Head of Office Adjunct Professors UiT –

Andrew Michael Teale Elina Associate Professor Melteig UiO Communication Advisor

Hylleraas annual report 104 2017 | 2018

Senior Engineers Scientific Advisory – Committee –

Michael Simen Chantal Repisky Reine Daniel (chair) UiT UiO Professor, Université de Strasbourg

Mauritz Osamu Serena Ryding Sekiguichi DeBeer UiO UiO Professor MPI Mülheim

Markus Reiher Professor ETH Zürich

Board of Directors Ursula – Röthlisberger Professor EPF Lausanne Jo Døhl Camilla (chair) Brekke Head of Professor Department Dept. Phys. Peter Dept. Chemistry Tech. Schmelcher UiO UiT Professor Universität Hamburg Atle Jensen Nathalie Professor Reuter Dept. Mathematics Professor UiO Dept. Bio. Sciences UiB

Kajsa Ryttberg-Wallgren VP Vacuum Conveying Division Piab Group, Sweden

Hylleraas annual report 2017 | 2018 105 Publications 2017/2018 – Publications 2017

1 5 9

Title: Cryptophanes for Methane and Title: Biomembrane solubilization mech- Title: Synthesis and Characterization of Encapsulation: A Comparative Density anism by Triton X-100: a computational Iridium(V) Coordination Complexes With an Functional Theory Study of Binding study of the three stage model N,O-Donor Organic Ligand Properties and NMR Chemical Shifts Author(s): Pizzirusso, A (Pizzirusso, Author(s): Sharninghausen, LS (Sharning- Author(s): Demissie, TB (Demissie, Taye Antonio); De Nicola, A (De Nicola, Antonio); hausen, Liam S.); Sinha, SB (Sinha, Shashi B.); Ruud, K (Ruud, Kenneth); Hansen, JH Sevink, GJA (Sevink, G. J. Agur); Correa, Bhushan); Shopov, DY (Shopov, Dimitar (Hansen, Jorn H.) A (Correa, Andrea); Cascella, M (Cascella, Y.); Mercado, BQ (Mercado, Brandon Q.); Source: JOURNAL OF PHYSICAL CHEM- Michele); Kawakatsu, T (Kawakatsu, Balcells, D (Balcells, David); Brudvig, GW ISTRY A Volume: 121 Issue: 50 Pages: Toshihiro); Rocco, M (Rocco, Mattia); Zhao, (Brudvig, Gary W.); Crabtree, RH (Crabtree, 9669-9677 DOI: 10.1021/acsjpca.7b10595 Y (Zhao, Ying); Celino, M (Celino, Massimo); Robert H.) Published: DEC 21 2017s Milano, G (Milano, Giuseppe) Source: ANGEWANDTE CHEMIE-INTERNA- Source: PHYSICAL CHEMISTRY CHEMICAL TIONAL EDITION Volume: 56 Issue: 42 2 PHYSICS Volume: 19 Issue: 44 Pages: Pages: 13047-13051 DOI: 10.1002/ 29780-29794 DOI: 10.1039/c7cp03871b anie.201707593 Published: OCT 9 2017s Title: Rhodium-Catalyzed Synthesis Published: NOV 28 2017s of Sulfur Ylides via in Situ Generated 10 lodonium Ylides 6 Author(s): Vaitla, J (Vaitla, Janakiram); Title: Connections between variation Hopmann, KH (Hopmann, Kathrin H.); Title: Interplay of twist angle and solvents principles at the interface of wave-function Bayer, A (Bayer, Annette) with two-photon optical channel interfer- and density-functional theories Source: ORGANIC LETTERS Volume: 19 ence in aryl-substituted BODIPY dyes Author(s): Irons, TJP (Irons, Tom J. P.); Issue: 24 Pages: 6688-6691 DOI: 10.1021/ Author(s): Alam, MM (Alam, Md. Mehboob); Furness, JW (Furness, James W.); Ryley, MS acs.orglett.7b03413 Published: DEC 15 2017s Misra, R (Misra, Ramprasad); Ruud, K (Ryley, Matthew S.); Zemen, J (Zemen, Jan); (Ruud, Kenneth) Helgaker, T (Helgaker, Trygve); Teale, AM 3 Source: PHYSICAL CHEMISTRY CHEMICAL (Teale, Andrew M.) PHYSICS Volume: 19 Issue: 43 Pages: Source: JOURNAL OF CHEMICAL PHYSICS Title: Molecular and Silica-Supported 29461-29471 DOI: 10.1039/c7cp05679f Volume: 147 Issue: 13 Article Number: Molybdenum Alkyne Metathesis Catalysts: Published: NOV 21 2017 s 134107 DOI: 10.1063/1.4985883 Published: Influence of Electronics and Dynamics on OCT 7 2017s Activity Revealed by Kinetics, Solid-State 7 NMR, and Chemical Shift Analysis 11 Author(s): Estes, DP (Estes, Deven P.); Title: Relativistic effects on the NMR Gordon, CP (Gordon, Christopher P.); Fe- parameters of Si, Ge, Sn, and Pb alkynyl Title: Anomalous Phosphorescence from an dorov, A (Fedorov, Alexey); Liao, WC (Liao, compounds: Scalar versus spin-orbit effects Organometallic White-Light Phosphor Wei-Chih); Ehrhorn, H (Ehrhorn, Henrike); Author(s): Demissie, TB (Demissie, Taye B.) Author(s): Paul, L (Paul, Lopa); Chakrabarti, Bittner, C (Bittner, Celine); Zier, ML (Zier, Source: JOURNAL OF CHEMICAL PHYSICS S (Chakrabarti, Swapan); Ruud, K (Ruud, Manuel Luca); Bockfeld, D (Bockfeld, Dirk); Volume: 147 Issue: 17 Article Number: Kenneth) Chan, KW (Chan, Ka Wing); Eisenstein, O 174301 DOI: 10.1063/1.4996712 Published: Source: JOURNAL OF PHYSICAL CHEMIS- (Eisenstein, Odile); Raynaud, C (Raynaud, NOV 7 2017s TRY LETTERS Volume: 8 Issue: 19 Pages: Christophe); Tamm, M (Tamm, Matthias); 4893-4897 DOI: 10.1021/acs.jpclett.7b02148 Coperet, C (Coperet, Christophe) 8 Published: OCT 5 2017s Source: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Volume: 139 Issue: Title: Addition and removal energies of 12 48 Pages: 17597-17607 DOI: 10.1021/ circular quantum dots jacs.7b09934 Title: Enantioselective Incorporation of CO : Published: DEC 6 2017s Author(s): Yuan, F (Yuan, Fei); Novario, 2 SJ (Novario, Samuel J.); Parzuchowski, NM Status and Potential (Parzuchowski, Nathan M.); Reimann, S Author(s): Vaitla, J (Vaitla, Janakiram); 4 (Reimann, Sarah); Bogner, SK (Bogner, Guttormsen, Y (Guttormsen, Yngve); S. K.); Hjorth-Jensen, M (Hjorth-Jensen, Mannisto, JK (Mannisto, Jere K.); Nova, Title: A competing, dual mechanism for Morten) A (Nova, Ainara); Repo, T (Repo, Timo); catalytic direct benzene hydroxylation from Bayer, A (Bayer, Annette); Hopmann, KH combined experimental-DFT studies Source: JOURNAL OF CHEMICAL PHYSICS Volume: 147 Issue: 16 Article Number: (Hopmann, Kathrin H.) Author(s): Vilella, L (Vilella, Laia); Conde, 164109 DOI: 10.1063/1.4995615 Published: Source: ACS CATALYSIS Volume: 7 A (Conde, Ana); Balcells, D (Balcells, David); OCT 28 2017s Issue: 10 Pages: 7231-7244 DOI: 10.1021/ Diaz-Requejo, MM (Diaz-Requejo, M. Mar); acscatal.7b02306 Published: OCT 2017 s Lledos, A (Lledos, Agusti); Perez, PJ (Perez, Pedro J.) Source: CHEMICAL SCIENCE Volume: 8 Issue: 12 Pages: 8373-8383 DOI: 10.1039/ c7sc02898a Published: DEC 1 2017s

Hylleraas annual report 2017 | 2018 107 Publications 2017/2018 –

13 15 17

Title: On Resolution-of-the-Identity Electron Title: DFT Investigation of Suzuki-Miyaura Title: One Electron Changes the Entire Repulsion Integral Approximations and Reactions with Aryl Sulfamates Using a Story: NMR versus pNMR Variational Stability Dialkylbiarylphosphine-Ligated Palladium Author(s): Demissie, TB (Demissie, Taye B.) Catalyst Author(s): Wirz, LN (Wirz, Lukas N.); Edited by: Simos TE; Kalogiratou Z; Reine, SS (Reine, Simen S.); Pedersen, TB Author(s): Melvin, PR (Melvin, Patrick R.); Monovasilis T Nova, A (Nova, Ainara); Balcells, D (Balcells, (Pedersen, Thomas Bondo) Source: Proceedings of the International David); Hazari, N (Hazari, Nilay); Tilset, Source: JOURNAL OF CHEMICAL THEORY Conference of Computational Methods M (Tilset, Mats) AND COMPUTATION Volume: 13 Issue: in Sciences and Engineering 2017 (ICCM- 10 Pages: 4897-4906 DOI: 10.1021/acs. Source: ORGANOMETALLICS Volume: 36 SE-2017) Book Series: AIP Conference jctc.7b00801 Published: OCT 2017s Issue: 18 Pages: 3664-3675 DOI: 10.1021/ Proceedings Volume: 1906 Article Number: acs.organomet.7b00642 Published: SEP 25 UNSP 030016 DOI: 10.1063/1.5012295 2017 s 14 Published: 2017 Accession Number: WOS:000419835900016 Title: Relation Between Ring Currents and 16 Conference Title: International Conference Hydrogenation Enthalpies for Assessing the of Computational Methods in Sciences and Degree of Aromaticity Title: Magnetic-Field Density-Functional Engineering (ICCMSE). Conference Date: Theory (BDFT): Lessons from the Adiabatic Author(s): Kumar, C (Kumar, Chandan); APR 21-25, 2017. Conference Location: Connection Fliegl, H (Fliegl, Heike); Sundholm, D Thessaloniki, GREECE. Conference (Sundholm, Dage) Author(s): Reimann, S (Reimann, Sarah); Sponsors: European Soc Computat Borgoo, A (Borgoo, Alex); Tellgren, EI Methods Sci & Engns Source: JOURNAL OF PHYSICAL CHEM- (Tellgren, Erik I.); Teale, AM (Teale, Andrew ISTRY A Volume: 121 Issue: 38 Pages: M.); Helgaker, T (Helgaker, Trygve) 18 7282-7289 DOI: 10.1021/acs.jpca.7b07607 Published: SEP 28 2017s Source: JOURNAL OF CHEMICAL THEORY AND COMPUTATION Volume: 13 Issue: 9 Title: Special issue in honour of Debashis Pages: 4089-4100 DOI: 10.1021/acs. Mukherjee Foreword jctc.7b00295 Published: SEP 2017s Author(s): Pal, S (Pal, Sourav); Helgaker, T (Helgaker, Trygve); Savin, A (Savin, Andreas) Source: MOLECULAR PHYSICS Volume: 115 Issue: 21-22 Special Issue: SI Pages: 2627- 2628 DOI: 10.1080/00268976.2017.1380450 Publications 2018 Published: 2017

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Title: A computational quantum-mechanical Title: Resolution-of-identity accelerated Title: An efficient pseudo-spectral method model of a molecular magnetic trap relativistic two- and four-component for the description of atomic electronic wave functions - Application to the Author(s): Adamowicz, L (Adamowicz, electron dynamics approach to chiroptical hydrogen atom in a uniform magnetic field Ludwik); Stanke, M (Stanke, Monika); spectroscopies Tellgren, E (Tellgren, Erik); Helgaker, T Author(s): Konecny, L (Konecny, Lukas); Author(s): Woywod, C (Woywod, Clemens); (Helgaker, Trygve) Kadek, M (Kadek, Marius); Komorovsky, S Roy, S (Roy, Susmita); Maiti, KS (Maiti, Kiran Sankar); Ruud, K (Ruud, Kenneth) Source: JOURNAL OF CHEMICAL PHYSICS (Komorovsky, Stanislav); Ruud, K (Ruud, Volume: 149 Issue: 24 Article Number: Kenneth); Repisky, M (Repisky, Michal) Source: CHEMICAL PHYSICS Volume: 244112 DOI: 10.1063/1.5055767 Published: Source: JOURNAL OF CHEMICAL PHYSICS 515 Pages: 299-314 DOI: 10.1016/j. DEC 28 2018 Volume: 149 Issue: 20 Article Number: chemphys.2018.09.025 Published: NOV 14 204104 DOI: 10.1063/1.5051032 Published: 2018 2 NOV 28 2018 6 Title: Iron-Catalyzed Carbenoid-Transfer 4 Reactions of Vinyl Sulfoxonium Ylides: An Title: Generalized Kohn-Sham iteration on Experimental and Computational Study Title: Nuclear magnetic moment of Banach spaces Author(s): Vaitla, J (Vaitla, Janakiram); Bi-209 from NMR experiments Author(s): Laestadius, A (Laestadius, Bayer, A (Bayer, Annette); Hopmann, KH Author(s): Antusek, A (Antusek, Andrej); Andre); Penz, M (Penz, Markus); Tellgren, (Hopmann, Kathrin H.) Repisky, M (Repisky, Michal); Jaszunski, EI (Tellgren, Erik I.); Ruggenthaler, M (Ruggenthaler, Michael); Kvaal, S (Kvaal, Source: ANGEWANDTE CHEMIE-INTER- M (Jaszunski, Michal); Jackowski, K Simen); Helgaker, T (Helgaker, Trygve) NATIONAL EDITION Volume: 57 Issue: (Jackowski, Karol); Makulski, W (Makulski, 49 Pages: 16180-16184 DOI: 10.1002/ Wlodzimierz); Misiak, M (Misiak, Maria) Source: JOURNAL OF CHEMICAL PHYSICS anie.201810451 Published: DEC 3 2018 Source: PHYSICAL REVIEW A Volume: Volume: 149 Issue: 16 Article Number: 98 Issue: 5 Article Number: 052509 DOI: 164103 10.1103/PhysRevA.98.052509 Published: DOI: 10.1063/1.5037790 Published: OCT NOV 19 2018 28 2018

Hylleraas annual report 108 2017 | 2018 7 11 15

Title: The activation of carbon dioxide by Title: Intersystem crossing rate dependent Title: The Key Role of the Hemiaminal Inter- first row transition metals (Sc-Zn) dual emission and phosphorescence from mediate in the Iron-Catalyzed Deaminative Author(s): Blaziak, K (Blaziak, Kacper); cyclometalated platinum complexes: a Hydrogenation of Amides Tzeli, D (Tzeli, Demeter); Xantheas, SS second order cumulant expansion based Author(s): Suarez, LA (Suarez, Lluis Artus); (Xantheas, Sotiris S.); Uggerud, E (Uggerud, approach Culakova, Z (Culakova, Zuzana); Balcells, Einar) Author(s): Moitra, T (Moitra, Torsha); Alam, D (Balcells, David); Bernskoetter, WH Source: PHYSICAL CHEMISTRY CHEMICAL MM (Alam, Md Mehboob); Chakrabarti, S (Bernskoetter, Wesley H.); Eisenstein, O PHYSICS Volume: 20 Issue: 39 Pages: (Chakrabarti, Swapan) (Eisenstein, Odile); Goldberg, KI (Goldberg, 25495-25505 DOI: 10.1039/c8cp04231d Source: PHYSICAL CHEMISTRY CHEMICAL Karen I.); Hazari, N (Hazari, Nilay); Tilset, M Published: OCT 21 2018 PHYSICS Volume: 20 Issue: 36 Pages: (Tilset, Mats); Nova, A (Nova, Ainara) 23244-23251 DOI: 10.1039/c8cp03111h Source: ACS CATALYSIS Volume: 8 Issue: 8 Published: SEP 28 2018 9 Pages: 8751-8762 DOI: 10.1021/acs- catal.8b02184 Published: SEP 2018 Title: Bethe-Salpeter correlation energies of 12 atoms and molecules 16 Author(s): Holzer, C (Holzer, Christof); Gui, Title: Rare and Nonexistent Nitrosyls: X (Gui, Xin); Harding, ME (Harding, Michael Periodic Trends and Relativistic Effects in Title: A fundamental catalytic difference E.); Kresse, G (Kresse, Georg); Helgaker, T Ruthenium and Osmium Porphyrin- Based between and manganese dependent (Helgaker, Trygve); Klopper, W (Klopper, {MNO}(7) Complexes enzymes revealed in a bacterial isatin Wim) Author(s): Demissie, TB (Demissie, Taye B.); hydrolase Source: JOURNAL OF CHEMICAL PHYSICS Conradie, J (Conradie, Jeanet); Vazquez-Li- Author(s): Sommer, T (Sommer, Theis); Volume: 149 Issue: 14 Article Number: ma, H (Vazquez-Lima, Hugo); Ruud, K Bjerregaard-Andersen, K (Bjerregaard-An- 144106 DOI: 10.1063/1.5047030 Published: (Ruud, Kenneth); Ghosh, A (Ghosh, Abhik) dersen, Kaare); Uribe, L (Uribe, Lalita); OCT 14 2018 Source: ACS OMEGA Volume: 3 Issue: 9 Etzerodt, M (Etzerodt, Michael); Diezemann, Pages: 10513-10516 DOI: 10.1021/acsome- G (Diezemann, Gregor); Gauss, J (Gauss, 9 ga.8b01434 Published: SEP 2018 Juergen); Cascella, M (Cascella, Michele); Morth, JP (Morth, J. Preben) Title: A local tensor that unifies kinetic 13 Source: SCIENTIFIC REPORTS Volume: 8 energy density and vorticity in density Article Number: 13104 DOI: 10.1038/s41598- functional theory Title: Polarizable Embedding Combined with 018-31259-y Published: AUG 30 2018 Author(s): Sen, S (Sen, Sangita); Tellgren, EI the Algebraic Diagrammatic Construction: (Tellgren, Erik I.) Tackling Excited States in Biomolecular 17 Source: JOURNAL OF CHEMICAL PHYSICS Systems Volume: 149 Issue: 14 Article Number: Author(s): Scheurer, M (Scheurer, Maxi- Title: Accelerating Kohn-Sham response 144109 DOI: 10.1063/1.5041931 Published: milian); Herbst, MF (Herbst, Michael F.); theory using density fitting and the OCT 14 2018 Reinholdt, P (Reinholdt, Peter); Olsen, JMH auxiliary-density-matrix method (Olsen, Jogvan Magnus Haugaard); Dreuw, Author(s): Kumar, C (Kumar, Chandan); 10 A (Dreuw, Andreas); Kongsted, J (Kongsted, Fliegl, H (Fliegl, Heike); Jensen, F (Jensen, Jacob) Frank); Teale, AM (Teale, Andrew M.); Title: Synthesis of a (N, C, C) Au(III) pincer Source: JOURNAL OF CHEMICAL THEORY Reine, S (Reine, Simen); Kjaergaard, T complex via C-sp3-H bond activation: AND COMPUTATION Volume: 14 Issue: (Kjaergaard, Thomas) increasing catalyst robustness by rational 9 Pages: 4870-4883 DOI: 10.1021/acs. Source: INTERNATIONAL JOURNAL OF catalyst design jctc.8b00576 Published: SEP 2018 QUANTUM CHEMISTRY Volume: 118 Issue: Author(s): Holmsen, MSM (Holmsen, 16 Article Number: e25639 DOI: 10.1002/ Marte Sofie Martinsen); Nova, A (Nova, 14 qua.25639 Published: AUG 15 2018 Ainara); Hylland, K (Hylland, Knut); Wragg, DS (Wragg, David S.); Oien-Odegaard, S Title: Hybrid Particle-Field Molecular 18 (Oien-Odegaard, Sigurd); Heyn, RH (Heyn, Dynamics Simulations of Charged Amphi- Richard H.); Tilset, M (Tilset, Mats) philes in an Aqueous Environment Title: Interplay of Through-Bond Hyperfine Source: CHEMICAL COMMUNICATIONS Author(s): Kolli, HB (Kolli, Hima Bindu); and Substituent Effects on the NMR Volume: 54 Issue: 79 Pages: 11104-11107 de Nicola, A (de Nicola, Antonio); Bore, Chemical Shifts in Ru(III) Complexes DOI: 10.1039/c8cc05489d Published: OCT SL (Bore, Sigbjorn Loland); Schafer, K Author(s): Jeremias, L (Jeremias, Lukas); 11 2018 (Schaefer, Ken); Diezemann, G (Diezemann, Novotny, J (Novotny, Jan); Repisky, M Gregor); Gauss, J (Gauss, Juergen); (Repisky, Michal); Komorovsky, S (Komor- Kawakatsu, T (Kawakatsu, Toshihiro); ovsky, Stanislav); Marek, R (Marek, Radek) Lu, ZY (Lu, Zhong-Yuan); Zhu, YL (Zhu, Source: INORGANIC CHEMISTRY Volume: You-Liang); Milano, G (Milano, Giuseppe); 57 Issue: 15 Pages: 8748-8759 DOI: Cascella, M (Cascella, Michele) 10.1021/acs.inorgchem.8b00073 Published: Source: JOURNAL OF CHEMICAL THEORY AUG 6 2018 AND COMPUTATION Volume: 14 Issue: 9 Pages: 4928-4937 DOI: 10.1021/acs. jctc.8b00466 Published: SEP 2018

Hylleraas annual report 2017 | 2018 109 Publications 2018 –

19 27 23 Title: Unraveling the Microscopic Origin of Title: Benchmarking the Performance Triplet Lasing from Organic Solids Title: Self-Assembly of alpha-Tocopherol of Exchange-Correlation Functionals Transfer Protein Nanoparticles: A Patchy Author(s): Paul, L (Paul, Lopa); Banerjee, A for Predicting Two-Photon Absorption Protein Model (Banerjee, Ambar); Paul, A (Paul, Ankan); Strengths Ruud, K (Ruud, Kenneth); Chakrabarti, S Author(s): Peltzer, RM (Peltzer, Raphael Author(s): Beerepoot, MTP (Beerepoot, (Chakrabarti, Swapan) Mathias); Kolli, HB (Kolli, Hima Bindu); Maarten T. P.); Alam, MM (Alam, Md. Stocker, A (Stocker, Achim); Cascella, M Source: JOURNAL OF PHYSICAL CHEMIS- Mehboob); Bednarska, J (Bednarska, (Cascella, Michele) TRY LETTERS Volume: 9 Issue: 15 Pages: Joanna); Bartkowiak, W (Bartkowiak, 4314-4318 DOI: 10.1021/acs.jpclett.8b02191 Source: JOURNAL OF PHYSICAL CHEM- Wojciech); Ruud, K (Ruud, Kenneth); Published: AUG 2 2018 ISTRY B Volume: 122 Issue: 28 Pages: Zalesny, R (Zalesny, Robert) 7066-7072 DOI: 10.1021/acs.jpcb.8b05936 Source: JOURNAL OF CHEMICAL THEORY Published: JUL 19 2018 20 AND COMPUTATION Volume: 14 Issue: 7 Pages: 3677-3685 DOI: 10.1021/acs. Title: Importance of Accurate Structures for 24 jctc.8b00245 Published: JUL 2018 Quantum Chemistry Embedding Methods: Which Strategy Is Better? Title: Bicycloaromaticity and Baird-type 28 bicycloaromaticity of dithienothio- Author(s): Kjellgren, ER (Kjellgren, Erik phene-bridged [34]octaphyrins Rosendahl); Olsen, JMH (Olsen, Jogvan Title: An acylation-Finkelstein approach to Magnus Haugaard); Kongsted, J (Kongsted, Author(s): Valiev, RR (Valiev, Rashid R.); radioiodination of bioactives: The role of Jacob) Fliegl, H (Fliegl, Heike); Sundholm, D amide group anchimeric assistance (Sundholm, Dage) Source: JOURNAL OF CHEMICAL THEORY Author(s): Fjellaksel, R (Fjellaksel, Richard); AND COMPUTATION Volume: 14 Issue: Source: PHYSICAL CHEMISTRY CHEMICAL Dugalic, D (Dugalic, Damir); Demissie, TB 8 Pages: 4309-4319 DOI: 10.1021/acs. PHYSICS Volume: 20 Issue: 26 Pages: (Demissie, Taye B.); Riss, PJ (Riss, Patrick jctc.8b00202 Published: AUG 2018 17705-17713 DOI: 10.1039/c8cp03112f J.); Hjelstuen, OK (Hjelstuen, Ole-Kristian); Published: JUL 14 2018 Sundset, R (Sundset, Rune); Hansen, JH (Hansen, Jorn H.) 21 25 Source: JOURNAL OF PHYSICAL ORGANIC Title: Rational Synthesis of Antiaromatic CHEMISTRY Volume: 31 Issue: 7 Article 5,15-Dioxaporphyrin and Oxidation into Title: Synthesis and Characterization of Number: e3835 DOI: 10.1002/poc.3835 beta,beta-Linked Dimers Stable Gold(III) PNP Pincer Complexes Published: JUL 2018 Author(s): Nishiyama, A (Nishiyama, Author(s): Grajeda, J (Grajeda, Javier); Akihide); Fukuda, M (Fukuda, Masaya); Nova, A (Nova, Ainara); Balcells, D (Balcells, 29 Mori, S (Mori, Shigeki); Furukawa, K David); Bruch, QJ (Bruch, Quinton J.); (Furukawa, Ko); Fliegl, H (Fliegl, Heike); Wragg, DS (Wragg, David S.); Heyn, RH Title: NMR chemical shift analysis decodes Furuta, H (Furuta, Hiroyuki); Shimizu, S (Heyn, Richard H.); Miller, AJM (Miller, olefin oligo- and polymerization activity of (Shimizu, Soji) Alexander J. M.); Tilset, M (Tilset, Mats) d(0) group 4 metal complexes Source: ANGEWANDTE CHEMIE-IN- Source: EUROPEAN JOURNAL OF Author(s): Gordon, CP (Gordon, Christopher TERNATIONAL EDITION Volume: 57 INORGANIC CHEMISTRY Issue: 26 Pages: P.); Shirase, S (Shirase, Satoru); Yamamoto, Issue: 31 Pages: 9728-9733 DOI: 10.1002/ 3113-3117 DOI: 10.1002/ejic.201800019 K (Yamamoto, Keishi); Andersen, RA anie.201804648 Published: JUL 26 2018 Published: JUL 13 2018 (Andersen, Richard A.); Eisenstein, O (Eisenstein, Odile); Coperet, C (Coperet, Christophe) 22 26 Source: PROCEEDINGS OF THE NATIONAL Title: Influence of a "Dangling" Co(II) Ion Title: Infrared, Raman and computational ACADEMY OF SCIENCES OF THE UNITED Bound to a [MnCo3O4] Oxo Cubane study of a crystalline mononuclear STATES OF AMERICA Volume: 115 Issue: complex of relevance to the pigment 26 Pages: E5867-E5876 DOI: 10.1073/ Author(s): Nguyen, AI (Nguyen, Andy, I); Verdigris pnas.1803382115 Published: JUN 26 2018 Darago, LE (Darago, Lucy E.); Balcells, D (Balcells, David); Tilley, TD (Tilley, T. Don) Author(s): Platania, E (Platania, Elena); Streeton, NLW (Streeton, Noelle L. W.); 30 Source: JOURNAL OF THE AMERICAN Kutzke, H (Kutzke, Hartmut); Karlsson, CHEMICAL SOCIETY Volume: 140 Issue: A (Karlsson, Arne); Uggerud, E (Uggerud, Title: Cobalt-catalysed hydro- 29 Pages: 9030-9033 DOI: 10.1021/ Einar); Andersen, NH (Andersen, Niels genation: a metallacycle can explain jacs.8b04065 Published: JUL 25 2018 Hojmark) the hydroxyl activating effect and the Source: VIBRATIONAL SPECTROSCOPY diastereoselectivity Volume: 97 Pages: 66-74 DOI: 10.1016/j. Author(s): Morello, GR (Morello, Glenn vibspec.2018.05.004 Published: JUL 2018 R.); Zhong, HY (Zhong, Hongyu); Chirik, PJ (Chirik, Paul J.); Hopmann, KH (Hopmann, Kathrin H.) Source: CHEMICAL SCIENCE Volume: 9 Issue: 22 Pages: 4977-4982 DOI: 10.1039/ c8sc01315b Published: JUN 14 2018

Hylleraas annual report 110 2017 | 2018 31 35 38

Title: Carbon-carbon bonds with CO2: Title: Theoretical and Experimental Study Title: Crystal Field in Rare-Earth Complexes: Insights from computational studies on the Reaction of tert-Butylamine with OH From Electrostatics to Bonding Author(s): Obst, M (Obst, Marc); Pavlovic, Radicals in the Atmosphere Author(s): Alessandri, R (Alessandri, L (Pavlovic, Ljiljana); Hopmann, KH Author(s): Tan, W (Tan, Wen); Zhu, L (Zhu, Riccardo); Zulfikri, H (Zulfikri, Habiburrah- (Hopmann, Kathrin H.) Liang); Mikoviny, T (Mikoviny, Tomas); man); Autschbach, J (Autschbach, Jochen); Source: JOURNAL OF ORGANOMETALLIC Nielsen, CJ (Nielsen, Claus J.); Wisthaler, Bolvin, H (Bolvin, Helene) CHEMISTRY Volume: 864 Special A (Wisthaler, Armin); Eichler, P (Eichler, Source: CHEMISTRY-A EUROPEAN Issue: SI Pages: 115-127 DOI: 10.1016/j. Philipp); Muller, M (Mueller, Markus); JOURNAL Volume: 24 Issue: 21 Pages: jorganchem.2018.02.020 Published: JUN 1 D'Anna, B (D'Anna, Barbara); Farren, NJ 5538-5550 DOI: 10.1002/chem.201705748 2018 (Farren, Naomi J.); Hamilton, JF (Hamilton, Published: APR 11 2018 Jacqueline F.); Pettersson, JBC (Pettersson, Jan B. C.); Hallquist, M (Hallquist, Mattias); 32 39 Antonsen, S (Antonsen, Simen); Stenstrom, Y (Stenstrom, Yngve) Title: Computational Studies of Aromatic Title: Combination of large and small basis and Photophysical Properties of Expanded Source: JOURNAL OF PHYSICAL CHEM- sets in electronic structure calculations on Porphyrins ISTRY A Volume: 122 Issue: 18 Pages: large systems 4470-4480 DOI: 10.1021/acs.jpca.8b01862 Author(s): Valiev, RR (Valiev, Rashid R.); Author(s): Roeggen, I (Roeggen, Inge); Gao, Published: MAY 10 2018 Benkyi, I (Benkyi, Isaac); Konyshev, YV B (Gao, Bin) (Konyshev, Yuri, V); Fliegl, H (Fliegl, Heike); Source: JOURNAL OF CHEMICAL PHYSICS 36 Sundholm, D (Sundholm, Dage) Volume: 148 Issue: 13 Article Number: Source: JOURNAL OF PHYSICAL CHEM- 134118 DOI: 10.1063/1.5018148 Published: Title: A Dinuclear Iridium(V,V) Oxo-Bridged ISTRY A Volume: 122 Issue: 20 Pages: APR 7 2018 Complex Characterized Using a Bulk 4756-4767 DOI: 10.1021/acs.jpca.8b02311 Electrolysis Technique for Crystallizing Published: MAY 24 2018 Highly Oxidizing Compounds 40 Author(s): Shopov, DY (Shopov, Dimitar 33 Title: Structural Origin of Metal Specificity Y.); Sharninghausen, LS (Sharninghausen, in Isatin Hydrolase from Labrenzia aggrega- Liam S.); Sinha, SB (Sinha, Shashi Bhushan); Title: Catalytic Adaptation of Psychrophilic ta Investigated by Computer Simulations Mercado, BQ (Mercado, Brandon Q.); Elastase Balcells, D (Balcells, David); Brudvig, GW Author(s): Uribe, L (Uribe, Lalita); Author(s): Socan, J (Socan, Jaka); Kazemi, (Brudvig, Gary W.); Crabtree, RH (Crabtree, Diezemann, G (Diezemann, Gregor); Gauss, M (Kazemi, Masoud); Isaksen, GV (Isaksen, Robert H.) J (Gauss, Juergen); Morth, JP (Morth, Jens Geir Villy); Brandsdal, BO (Brandsdal, Bjorn Preben); Cascella, M (Cascella, Michele) Source: INORGANIC CHEMISTRY Volume: Olav); Aqvist, J (Aqvist, Johan) 57 Issue: 9 Pages: 5684-5691 DOI: 10.1021/ Source: CHEMISTRY-A EUROPEAN Source: BIOCHEMISTRY Volume: 57 Issue: acs.inorgchem.8b00757 Published: MAY 7 JOURNAL Volume: 24 Issue: 20 Special 20 Pages: 2984-2993 DOI: 10.1021/acs. 2018 Issue: SI Pages: 5074-5077 DOI: 10.1002/ biochem.8b00078 Published: MAY 22 2018 chem.201705159 Published: APR 6 2018

37 34 41 Title: Divide-Expand-Consolidate Title: Non-perturbative calculation of orbital Second-Order Moller-Plesset Theory with Title: Magnetically Induced Ring-Current and spin effects in molecules subject to Periodic Boundary Conditions Strengths in Mobius Twisted Annulenes non-uniform magnetic fields Author(s): Rebolini, E (Rebolini, Elisa); Author(s): Wirz, LN (Wirz, Lukas N.); Author(s): Sen, S (Sen, Sangita); Tellgren, EI Baardsen, G (Baardsen, Gustav); Hansen, Dimitrova, M (Dimitrova, Maria); Fliegl, H (Tellgren, Erik I.) AS (Hansen, Audun Skau); Leikanger, KR (Fliegl, Heike); Sundholm, D (Sundholm, Source: JOURNAL OF CHEMICAL PHYSICS (Leikanger, Karl R.); Pedersen, TB (Peders- Dage) Volume: 148 Issue: 18 Article Number: en, Thomas Bondo) Source: JOURNAL OF PHYSICAL CHEMIS- 184112 DOI: 10.1063/1.5029431 Published: Source: JOURNAL OF CHEMICAL THEORY TRY LETTERS Volume: 9 Issue: 7 Pages: MAY 14 2018 AND COMPUTATION Volume: 14 Issue: 1627-1632 DOI: 10.1021/acs.jpclett.8b00440 5 Pages: 2427-2438 DOI: 10.1021/acs. Published: APR 5 2018 jctc.8b00021 Published: MAY 2018

Hylleraas annual report 2017 | 2018 111 Publications 2018 –

42 46 50

Title: Designing Pd and Ni Catalysts for Title: Demonstrating that the nonorthogonal Title: Density-wave-function mapping in Cross-Coupling Reactions by Minimizing orbital optimized coupled cluster model degenerate current-density-functional Off-Cycle Species converges to full configuration interaction theory Author(s): Balcells, D (Balcells, David); Author(s): Myhre, RH (Myhre, Rolf H.) Author(s): Laestadius, A (Laestadius, Nova, A (Nova, Ainara) Source: JOURNAL OF CHEMICAL PHYSICS Andre); Tellgren, EI (Tellgren, Erik I.) Source: ACS CATALYSIS Volume: 8 Issue: Volume: 148 Issue: 9 Article Number: Source: PHYSICAL REVIEW A Volume: 4 Pages: 3499-3515 DOI: 10.1021/acs- 094110 DOI: 10.1063/1.5006160 Published: 97 Issue: 2 Article Number: 022514 DOI: catal.8b00230 Published: APR 2018 MAR 7 2018 10.1103/PhysRevA.97.022514 Published: FEB 23 2018 43 47 51 Title: Intramolecular structural parameters Title: Geometric Energy Derivatives at the are key modulators of the gel-liquid Complete Basis Set Limit: Application to the Title: Universal lower bounds on the kinetic transition in coarse grained simulations of Equilibrium Structure and Molecular Force energy of electronic systems with noncol- DPPC and DOPC lipid bilayers Field of Formaldehyde linear magnetism Author(s): Jaschonek, S (Jaschonek, Author(s): Morgan, WJ (Morgan, W. James); Author(s): Tellgren, EI (Tellgren, Erik I.) Stefan); Cascella, M (Cascella, Michele); Matthews, DA (Matthews, Devin A.); Source: PHYSICAL REVIEW A Volume: Gauss, J (Gauss, Juergen); Diezemann, G Ringholm, M (Ringholm, Magnus); Agarwal, 97 Issue: 2 Article Number: 022513 DOI: (Diezemann, Gregor); Milano, G (Milano, J (Agarwal, Jay); Gong, JZ (Gong, Justin Z.); 10.1103/PhysRevA.97.022513 Published: Giuseppe) Ruud, K (Ruud, Kenneth); Allen, WD (Allen, FEB 22 2018 Wesley D.); Stanton, JF (Stanton, John F.); Source: BIOCHEMICAL AND BIOPHYSICAL Schaefer, HF (Schaefer, Henry F., III) RESEARCH COMMUNICATIONS Volume: 52 498 Issue: 2 Special Issue: SI Pages: Source: JOURNAL OF CHEMICAL THEORY 327-333 DOI: 10.1016/j.bbrc.2017.10.132 AND COMPUTATION Volume: 14 Issue: Title: Metal alkyls programmed to generate Published: MAR 29 2018 3 Pages: 1333-1350 DOI: 10.1021/acs. metal alkylidenes by alpha-H abstraction: jctc.7b01138 Published: MAR 2018 prognosis from NMR chemical shift 44 Author(s): Gordon, CP (Gordon, Christopher 48 P.); Yamamoto, K (Yamamoto, Keishi); Title: Rhodium-Catalyzed Hydrocarboxyla- Searles, K (Searles, Keith); Shirase, S tion: Mechanistic Analysis Reveals Unusual Title: Density-Dependent Formulation of (Shirase, Satoru); Andersen, RA (Andersen, Transition State for Carbon-Carbon Bond Dispersion-Repulsion Interactions in Hybrid Richard A.); Eisenstein, O (Eisenstein, Formation Multiscale Quantum/Molecular Mechanics Odile); Coperet, C (Coperet, Christophe) (QM/MM) Models Author(s): Pavlovic, L (Pavlovic, Ljiljana); Source: CHEMICAL SCIENCE Volume: 9 Vaitla, J (Vaitla, Janakiram); Bayer, A (Bayer, Author(s): Curutchet, C (Curutchet, Carles); Issue: 7 Pages: 1912-1918 DOI: 10.1039/ Annette); Hopmann, KH (Hopmann, Kathrin Cupellini, L (Cupellini, Lorenzo); Kongsted, J c7sc05039a Published: FEB 21 2018 H.) (Kongsted, Jacob); Corni, S (Corni, Stefano); Frediani, L (Frediani, Luca); Steindal, AH Source: ORGANOMETALLICS Volume: 37 53 Issue: 6 Pages: 941-948 DOI: 10.1021/acs. (Steindal, Arnfinn Hykkerud); Guido, CA (Guido, Ciro A.); Scalmani, G (Scalmani, organomet.7b00899 Published: Title: A theoretical and experimental Giovanni); Mennucci, B (Mennucci, MAR 26 2018 benchmark study of core-excited states in Benedetta) Source: JOURNAL OF CHEMICAL THEORY 45 Author(s): Myhre, RH (Myhre, Rolf H.); AND COMPUTATION Volume: 14 Issue: Wolf, TJA (Wolf, Thomas J. A.); Cheng, L 3 Pages: 1671-1681 DOI: 10.1021/acs. Title: C-C Bond Formation of Mg- and (Cheng, Lan); Nandi, S (Nandi, Saikat); jctc.7b00912 Published: MAR 2018 Zn-Activated Carbon Dioxide Coriani, S (Coriani, Sonia); Guhr, M (Guhr, Author(s): Miller, GBS (Miller, Glenn B. S.); Markus); Koch, H (Koch, Henrik) 49 Uggerud, E (Uggerud, Einar) Source: JOURNAL OF CHEMICAL PHYSICS Source: CHEMISTRY-A EUROPEAN Volume: 148 Issue: 6 Article Number: Title: Cyclometalated ruthenium complexes JOURNAL Volume: 24 Issue: 18 Pages: 064106 DOI: 10.1063/1.5011148 Published: with carboxylated ligands from a combined 4710-4717 DOI: 10.1002/chem.201706069 FEB 14 2018 experimental/computational perspective Published: MAR 26 2018 Author(s): Thoresen, EM (Thoresen, Eirik Mydske); Balcells, D (Balcells, David); Oien-Odegaard, S (Oien-Odegaard, Sigurd); Hylland, KT (Hylland, Knut Tormodssonn); Tilset, M (Tilset, Mats); Amedjkouh, M (Amedjkouh, Mohamed) Source: DALTON TRANSACTIONS Volume: 47 Issue: 8 Pages: 2589-2601 DOI: 10.1039/ c7dt03935b Published: FEB 28 2018

Hylleraas annual report 112 2017 | 2018 54 58 62

Title: Inclusion of orbital relaxation and Title: Uniform magnetic fields in densi- Title: ANALYSIS OF THE EXTENDED correlation through the unitary group ty-functional theory COUPLED-CLUSTER METHOD IN QUAN- adapted open shell coupled cluster theory Author(s): Tellgren, EI (Tellgren, Erik I.); TUM CHEMISTRY using non-relativistic and scalar relativistic Laestadius, A (Laestadius, Andre); Helgaker, Author(s): Laestadius, A (Laestadius, Hamiltonians to study the core ionization T (Helgaker, Trygve); Kvaal, S (Kvaal, Andre); Kvaal, S (Kvaal, Simen) potential of molecules containing light to Simen); Teale, AM (Teale, Andrew M.) Source: SIAM JOURNAL ON NUMERICAL medium-heavy elements Source: JOURNAL OF CHEMICAL PHYSICS ANALYSIS Volume: 56 Issue: 2 Pages: 660- Author(s): Sen, S (Sen, Sangita); Shee, A Volume: 148 Issue: 2 Article Number: 683 DOI: 10.1137/17M1116611 Published: (Shee, Avijit); Mukherjee, D (Mukherjee, 024101 DOI: 10.1063/1.5007300 Published: 2018 Debashis) JAN 14 2018 Source: JOURNAL OF CHEMICAL PHYSICS 63 Volume: 148 Issue: 5 Article Number: 59 054107 DOI: 10.1063/1.5018086 Published: Title: Excitation energies from Gorling-Levy FEB 7 2018 Title: Density-functional theory for internal perturbation theory along the range-sepa- magnetic fields rated adiabatic connection 55 Author(s): Tellgren, EI (Tellgren, Erik I.) Author(s): Rebolini, E (Rebolini, Elisa); Source: PHYSICAL REVIEW A Volume: Teale, AM (Teale, Andrew M.); Helgaker, Title: Unimolecular dissociation of anions 97 Issue: 1 Article Number: 012504 DOI: T (Helgaker, Trygve); Savin, A (Savin, derived from succinic acid (H(2)Su) in the 10.1103/PhysRevA.97.012504 Published: Andreas); Toulouse, gas phase: HSu(-) and ClMgSu(center dot)(-) JAN 12 2018 J (Toulouse, Julien) Relationship to CO fixation 2 Source: MOLECULAR PHYSICS Volume: Author(s): Jestila, JS (Jestila, Joakim S.); 60 116 Issue: 11 Pages: 1443-1451 DOI: Uggerud, E (Uggerud, Einar) 10.1080/00268976.2017.1422811 Published: Source: EUROPEAN JOURNAL OF MASS Title: A Sterically Driven Approach to 2018 SPECTROMETRY Volume: 24 Issue: 1 Pag- the Efficient Synthesis of Low-Symmetry es: 33-42 DOI: 10.1177/1469066717729904 1,4-Diazepinoporphyrazines Part: 2 Published: FEB 2018 Author(s): Tarakanov, PA (Tarakanov, Pavel 56 A.); Simakov, AO (Simakov, Anton O.); Tarakanova, EN (Tarakanova, Ekaterina Title: Hybrid Particle-Field Model for N.); Chernyak, AV (Chernyak, Alexander Conformational Dynamics of Peptide Chains V.); Klykov, V (Klykov, Vladislav); Stuzhin, Author(s): Bore, SL (Bore, Sigbjorn Loland); PA (Stuzhin, Pavel A.); Pushkarev, VE Milano, G (Milano, Giuseppe); Cascella, M (Pushkarev, Victor E.) (Cascella, Michele) Source: MACROHETEROCYCLES Volume: Source: JOURNAL OF CHEMICAL THEORY 11 Issue: 3 Pages: 312-315 DOI: 10.6060/ AND COMPUTATION Volume: 14 Issue: mhc180484t Published: 2018 2 Pages: 1120-1130 DOI: 10.1021/acs. jctc.7b01160 Published: FEB 2018 61

57 Title: Naming polyhedra by general face-spirals - Theory and applications to Title: Dual fluorescence of (E)-N-(4-(di- and other polyhedral molecules methylamino)benzylidene)-2H-1,2,4-triazol- Author(s): Wirz, LN (Wirz, Lukas N.); 3-amine (DMABA-Amtr): A ground state Schwerdtfeger, P (Schwerdtfeger, Peter); perspective Avery, JE (Avery, James E.) Author(s): Mengesha, ET (Mengesha, Source: FULLERENES NANOTUBES Ephriem T.); Demissie, TB (Demissie, Taye AND CARBON NANOSTRUCTURES B.); Redi-Abshiro, M (Redi-Abshiro, Mesfin); Volume: 26 Issue: 10 Pages: 607-630 DOI: Mohammed, AM (Mohammed, Ahmed M.) 10.1080/1536383X.2017.1388231 Published: Source: SPECTROCHIMICA ACTA PART 2018 A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY Volume: 189 Pages: 601-607 DOI: 10.1016/j.saa.2017.08.070 Published: JAN 15 2018

Hylleraas annual report 2017 | 2018 113 Total Revenue and Expenditure Figures –

Hylleraas annual report 114 2017 | 2018 Actual financing of all academic activity at the Centre (in NOK thousand) 2017 2018

Financing agreed in the contract and reported in eRapport, but partly under other funding categories

Own funding 939 9 869

The Research Council (COE grant) 1 875 14 121

Total funding of the center as agreed in the contract ("basic financing") 2 814 23 990

Funding of projects with academic affiliation to the Centre

Other funding from the Research Council 11 952 16 334

International funding 0 5 887

Public funding 0 405

Private funding 4 287 4 546

Total funding from external projects ("additional funding") 16 239 27 172

Funding of total academic activity 19 053 51 162

Hylleraas annual report 2017 | 2018 115 Staff Report 2017 2018

Personnel resources in man-years 13.2 50.8 Professors and researchers 4.0 14.4 PhD Candidates 4.8 19.3 Postdoctoral Fellows 2.5 9.3 Visiting Researchers 0.9 3.6 Administrative and technical staff 1.0 4.2

Hylleraas annual report 116 2017 | 2018 “Every attempt to employ mathematical methods in the study of chemical questions must be considered profoundly irrational. If mathematical analysis should ever hold a prominent place in chemistry – an aberration which is happily impossible – it would occasion a rapid and widespread degradation of that science.”

Auguste Comte (1798–1857)

“The more progress sciences make, the more they tend to enter the domain of mathematics, which is a kind of center to which they all converge. We may even judge the degree of perfection to which a science has arrived by the facility with which it may be submitted to calculation.” Adolphe Quetelet (1796–1874) “What hold the countless atoms and molecules together in the large complexes we call matter are nothing but electrical forces – in a sense, everything is electricity. I know this sounds weird – but you get used to the idea, it eventually becomes natural. But don’t show this to anybody – lest they think I have become a bit odd.”

Egil A. Hylleraas (1898 – 1965), in letter to his brother Ottar Andersen in 1927

Hylleraas annual report 118 2017 | 2018 Design: Anagram Design Contact Information web pages: hylleraas.no email: [email protected]

Postal address Oslo: Postal address Tromsø: Hylleraas Centre Hylleraas Centre Department of Chemistry Department of Chemistry University of Oslo UiT The Arctic University of Norway P. O. Box 1033 Blindern P. O. Box 6050 Langnes N-0315 Oslo N-9037 Tromsø Norway Norway