Journal of Chemical Sciences [Formerly: Proceedings (Chemical Sciences)] Vol. 124, No. 1, January 2012 CONTENTS Special issue on Structure, Reactivity and Dynamics

Foreword ...... 11–12

3 Dynamics of atom tunnelling in a symmetric double well coupled to 2 an asymmetric double well: The case of malonaldehyde

1 –

> S Ghosh and S P Bhattacharyya ...... 13 19 x

-2 -2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 2.0

Shape change as entropic phase transition: A study using Jarzynski 0.2 relation Moupriya Das, Debasish Mondal and Deb Shankar Ray . . . . . 21–28

Y 0.0 Shape of a system plays an important role in non-equilibrium transitions between two thermalized states when the system size is finite. It is shown that -0.2 modulation of the shape of an enclosure may make the resident Brownian particles feel an entropic phase transition. -1.2 -0.6 0.0 0.6 1.2 X

Fitness landscapes in natural rocks system evolution: A conceptual DFT treatment

Fe2O3 χ 6 oxides (eV) 8 Soma Duley, Jean-Louis Vigneresse 5 Al2O3 SiO 2 TiO2 – 4 MgO and Pratim Kumar Chattaraj ...... 29 34 FeO 7 (eV) 7 ω minerals MnO CuS2O 3 3 Cu(SH) 6 6 2 Density functional theory provides the chemical reactivity descriptors, CaO CuSO3 Cu(OH) SH- 2 5 5 Cu2S2O3 2 SO3 (eV) CuS ω Cu2SO 3 CuO (electronegativity, hardness and electrophilicity) of major oxides as observed in Na2O S SO 4 4 2 2 Cu(SH) K O Cu2S 1 2 Cu(OH) natural igneous rocks. They are plotted within a fitness landscape diagram, with 3 3 Cu2SO2 Cu2O CuSO 2 0 2 the principles of minimum electrophilicity (MEP) and maximum hardness 0 1 2 3 4 5 6 2 3 4 5 6 7 η (eV) η (eV) (MHP) as guides towards the region of higher stability. Natural rocks evolve (a) (b) within the three poles of silica (SiO2), alkalis (K2O and Na2O) and redox agent (Fe3O2). An application to S-bearing copper compounds is also presented.

Hydrogen bonded networks in formamide [HCONH2]n (n =1− 10) clusters: A computational exploration of preferred aggregation patterns A Subha Mahadevi, Y Indra Neela and G Narahari Sastry .....35–42

Manifestation of hydrogen bond cooperativity as a function of increasing cluster size and varying arrangement of molecules is explored using formamide [HCONH2]n (n = 1 – 10) clusters based on DFT calculations.

1 2 Contents

Useofanintensemicrowavelasertodissociateadiatomic molecule: Theoretical prediction of dissociation dynamics

Amita Wadehra and B M Deb ...... 43–50

Taking the CO molecule as a Morse oscillator, the quantum dynamics of its dissociation under an intense microwave laser is followed theoretically and computationally. The time-dependent probability density is examined along with high-order harmonics generation and above-threshold dissociation.

TDDVR (a) A quantum-classical simulation of a multi-surface multi-mode + nuclear dynamics on C6H6 incorporating degeneracy among electronic states MCTDH (b) Subhankar Sardar and Satrajit Adhikari...... 51–58 Intensity

Experiment (c) The photoelectron spectra of benzene is quantum - classically simulated using parallelized time dependent discrete variable representation (TDDVR) method, where the degeneracy among different states is considered in the realistic model Hamiltonian of corresponding system. 11.4 11.6 11.8 12.0 12.2 Energy (eV) 2 2 + B E2g A2u band of C6 H6

Understanding proton affinity of tyrosine sidechain in hydrophobic confinement

T G Abi, T Karmakar and S Taraphder ...... 59–63

A density functional study is presented on the effect of hydrophobic confinement on the proton affinity of a tyrosine sidechain suspended within a single-walled carbon nanotube. The bulky sidechain encounters unfavorable steric interactions with the surrounding wall that primarily determines the observed lower reactivity of the sidechain.

1e-11 Full dimensional quantum scattering study of the H2 + CN reaction H2 (v1) + CN (v2) HCN + H 1e-12 S Bhattacharya, A Kirwai, Aditya N Panda 1e-13 /s] – 3 and H-D Meyer ...... 65 73 [cm k 1e-14 Present (v1v2)=(10) Present (v1v2)=(01) Rate constants for the H2 + CN reaction are presented for the reagents in their Ref. 29 (v1v2)=(00) 1e-15 Expt Ref. 6 (v1v2)=(01) excited vibrational states by carrying out exact wave packet studies using Expt Ref. 2 (v1v2)=(01) Ref. 28 (v1v2)=(10) multiconfiguration time dependent Hartree method. Ref. 28(v1v2)=(01) 1e-16 1 2 3 4 5 1000/T[1/K]

Dynamics of atomic clusters in intense optical fields of ultrashort duration

Deepak Mathur and Firoz A Rajgara ...... 75–81

Intense, 10 fs long laser pulses have been used to irradiate gas-phase Ar15,000 clusters. When multiply ionized, these clusters Coulomb explode, producing fast Ar-ions. The strong-field, few-cycle dynamics produce different angle- dependent ion energy and ion yield functions from those in the longer pulse (>30 fs) regime. Contents 3

Bhageerath—Targeting the near impossible: Pushing the frontiers of atomic models for protein tertiary structure prediction B Jayaram, Priyanka Dhingra, Bharat Lakhani and Shashank Shekhar ...... 83–91

Sequence to structure prediction is made using Bhageerath and Bhageerath-H method.

5 10 Quenching vibrations by collisions in cold traps: A quantum study vi=1 v =2 + 1 + 4 1 4 i 10 for MgH (X @ )with He( S) vi=3

vi=4 v =5

) i 2 3 10 D Caruso, M Tacconi, F A Gianturco and E Yurtsever ...... 93–97

2 10 +

Cross Section (Å The quenching process of the MgH vibrational energy induced by collisions

1 with He has been characterized by extensive ab initio quantum calculations. 10

+ + MgH (v=v )+He -> MgH (v=0) + He 0 i 10 -3 -2 -1 0 10 10 10 10 Collision Energy (K˚)

Design of optimal laser pulses to control molecular rovibrational excitation in a heteronuclear diatomic molecule Sitansh Sharma, Gabriel G Balint-Kurti and Harjinder Singh ...... 99–104

State selective control of vibrational and rotational molecular dynamics in HF by optimally designed laser pulses with high yields is reported.

Partition function of the two-dimensional nearest neighbour Ising models for finite lattices in a non-zero magnetic field M Vinothkumar, G Nandhini and M V Sangaranarayanan . . 105–113

The variation of the specific heat with nearest neighbour interaction energies for various magnetic fields pertaining to a square lattice of 64 sites is evaluated.

Dynamics study of a three-fold pseudo-Jahn–Teller system using the extended Longuet–Higgins formalism Biplab Sarkar and A J C Varandas ...... 115–120

Extended–Longuet–Higgins formalism provides a simple way to include the geometrical phase in the generalized Born–Oppenheimer equations of a three-fold Jahn–Teller system. 4 Contents

Optimal control of the initiation of a pericyclic reaction in the electronic ground state Timm Bredtmann and Jörn Manz ...... 121–129

How to initiate a pericyclic reaction in the electronic ground state? An attempt is made to solve the problem by means of Optimal Control Theory by designing an optimal laser pulse with down-chirped pump-dump sub-pulses in the ultraviolet frequency and sub-10 femtosecond time domains. The theoretical approach is supported by experimental results.

Structure and intermolecular vibrations of 7-azaindole-water 2:1 complex in a supersonic jet expansion: Laser-induced fluorescence spectroscopy and quantum chemistry calculation Montu K Hazra, Moitrayee Mukherjee, V Ramanathan and Tapas Chakraborty ...... 131–139

We have measured the low-frequency intermolecular vibrations of a 2:1 complex between 7-azaindole and water using laser-induced fluorescence spectroscopy in a supersonic jet expansion. The structure of the complex has been suggested by analysing these vibrations with the aid of the predictions of quantum chemistry calculation.

e-F2 Scattering e-HCl Scattering 0.07 Vibrational excitation resulting from electron capture in LUMO of 14 NWE F2 and HCl – A treatment using the time-dependent wave packet 0.06 LCP-TDWP 12 LCP-TDWP approach 0.05 10 ) )

2 0.04 2

(Å (Å 8 Bhavesh K Shandilya, Manabendra Sarma, Satrajit Adhikari

1←0 0.03 1←0 σ σ Exp 6 and Manoj K Mishra ...... 141–148 0.02 4 Houfek et al. Bardsey et al. 0.01 2 The vibrational excitation cross-sections in e-F2 and e-HCl scattering have been BO-NWE 0 0 calculated with local complex potential based time dependent wave packet 0 0.02 0.04 0.06 0.08 0.1 0.3 0.4 0.5 0.6 0.7 0.8 0.9 Energy (Hartree) Energy (eV) approach and compared with those of other theoretical/experimental results.

Tailoring approach for obtaining molecular orbitals of large systems

Anuja P Rahalkar and Shridhar R Gadre ...... 149–158

Molecular tailoring approach, a fragment-based method, is employed for obtaining the complete set of MOs, for large molecular systems, without performing the calculation on the whole system. The benchmarks are performed on the diverse molecules including :-conjugated systems at HF and DFT levels of theory.

Variation of diffusivity with the cation radii in molten salts of -18.3 (b) T = 1000K; Ag+ σ = 0.33 Å ( E = 16.214 kJ/mol ) superionic conductors containing iodine anion: A molecular cation A -18.4 σ = 0.53 Å ( E = 14.022 kJ/mol ) 0.8 cation A dynamics study Ag+ -18.5 /s )

2 0.75 m

-8 Srinivasa R Varanasi and S Yashonath ...... 159–166 ln D -18.6 0.7 D ( x 10 -18.7 Diffusivity exhibits a maximum when cation radius is varied in a molten salt 0.65 -18.8 containing iodide anion. Computed properties include radial distribution

0.6 function, diffusivity of cation and anion, velocity autocorrelation function, 0.32 0.4 0.48 0.56 0.64 0.9 0.95 1 1.05 1.1 σ -1 activation energy and intermediate scattering function. The results suggest that cation ( Å ) 1000/T (K ) the anomalous maximum arises from the Levitation Effect. Contents 5

Evidence for the powerful catalytic ability of imidozirconocene complex from its epoxide ring cleavage reactions – ADFT mechanistic view

Dhurairajan Senthilnathan, Rajadurai Vijay Solomon and Ponnambalam Venuvanalingam ...... 167–176

DFT calculations provide clear evidence for the bifunctional reactivity of imidozirconocene through bonding changes in the ring cleavage of epoxides Cyclooctene epoxide undergoes elimination and norbornene oxide follows insertion. Surprisingly, cyclohexene oxide which has both β positions blocked by methyl groups undergoes elimination instead of insertion due to carbocation Concerted TS stability.

Basic principles of ultrafast Raman loss spectroscopy

N K Rai, A Y Lakshmanna, V V Namboodiri and S Umapathy...... 177–186

The fundamentals of non-linear optical spectroscopy are presented. The theory is extended to understand the third order non-linear Raman spectroscopic techniques named as stimulated Raman spectroscopies. A systematic method to describe the Ultrafast Raman loss spectroscopy (URLS), a third ordered non- linear Raman process, is also presented.

Hydrogenoid orbitals revisited: From Slater orbitals to Coulomb Sturmians

Danilo Calderini, Simonetta Cavalli, Cecilia Coletti, Gaia Grossi and Vincenzo Aquilanti...... 187–192

The connection between the venerable Slater orbitals in quantum chemistry and the Coulomb Sturmain orbitals is pointed. An account of recent progress is outlined with reference to their relationships with the momentum space and hyperspherical harmonics representations.

The role of C–H...π interaction in the stabilization of benzene and adamantane clusters

R Mahesh Kumar, M Elango, R Parthasarathi, Dolly Vijay and V Subramanian ...... 193–202

Various possible modes of interaction between adamantane and benzene have been studied using ab intio and density functional theory based methods. It is found that adamantane can interact with four benzene rings through C–H…π interactions.

Density functional studies of endosulphan and its interaction with glycine and GABA

C N Ramachandran, Brijesh Kumar Mishra and Ashwani Kumar Tiwari...... 203–207

Interactions between various conformers of the organo-chloro pesticide endosulphan and the amino acids (glycine and GABA) have been studied using the MP2 and density functional methods. The results indicated that endosulphan binds strongly with both glycine and GABA. In addition to the one strong hydrogen bond, several weak interactions (C–H…O and C–H...N) participate in stabilizing the complex. 6 Contents

Variation of kinetic isotope effect in multiple proton transfer reactions

B Saritha and M Durga Prasad ...... 209–214

Kinetic isotope effect in multiple proton transfer reactions is investigated with specific reference to three systems, (HF)3,(H2O)n clusters and formic acid dimer.

Hydrogen bond dynamics and vibrational spectral diffusion in aqueous solution of acetone: A first principles molecular dynamics study

Bhabani S Mallik and ...... 215–221

Vibrational spectral diffusion and hydrogen bond dynamics in aqueous solution containing an acetone molecule are studied through ab initio molecular dynamics simulations and time series analysis. The present theoretical results are also compared with those of available experiments and classical simulations.

Fock-space multi-reference coupled-cluster response with the effect of triples on dipole moment of ClO and SF radicals

Lalitha Ravichandran, Debarati Bhattacharya, Nayana Vaval and ...... 223–232

Dipole moment calculations of SF and ClO radicals have been carried out using the partial triples correction in FSMRCC method. Dipole moments of these radicals are extremely sensitive to correlation effects. A brief insight to the way the triples correction has been implemented is presented. Analytic results are compared with ROHF calculations.

Excitation energy transfer from dye molecules to doped graphene

R S Swathi and K L Sebastian ...... 233–240

We had reported earlier that graphene is a very efficient quencher of the electronically excited states with the rate proportional to (distance)j4. In this paper, we predict a crossover of the distance dependence of the rate from power law to exponential as the Fermi level is increasingly shifted into the conduction band.

Scaling properties of net information measures for bound states of spherical model potentials confined with finite barrier

S H Patil and K D Sen ...... 241–245

The scaling of the sum of Shannon information entropy, ST, with the nuclear charge, Z, for the hydrogen isoelectronic series confined inside an impenetrable cavity of radius R . The optimum value of ST remains fixed for all Z, while the location of Ropt scales as 1/Z. Contents 7

Quantum dynamical study of low-energy photoelectron bands of 2-phenylethyl-N,N-dimethylamine

Susana Gomez-Carrasco and Horst Köppel ...... 247–253

Vertical ionization spectrum of PENNA along with the underlying orbitals are presented.

Computational investigation of hydrogen adsorption in silicon– lithium binary clusters

H2 Naresh K Jena, K Srinivasu and Swapan K Ghosh ...... 255–260

Silicon–lithium binary clusters have been investigated for their hydrogen adsorption properties through ab initio based density functional theory + Si5Li7 calculations. All the lithium sites in these clusters are found to be cationic in + Si5Li7 (H2)17 nature and can trap molecular hydrogen with a gravimetric density range of 13–15 wt%.

Structure and transport properties of LiF–BeF2 mixtures: Comparison of rigid and polarizable ion potentials

B Shadrack Jabes, Manish Agarwal and ...... 261–269

Behaviour of ionic conductivity as a function of temperature, calculated using a rigid ion model is compared with experiment and with a polarizable ion model for the LiF–BeF2 system at 33 mole% BeF2. Simulation snapshots of the LiF– BeF2 melt at concentrations of 10 and 70 mole% BeF2 along the 1500K isotherm are shown on the right. The green, blue and red coloured spheres represent the lithium, beryllium and fluorine, respectively.

Dynamics of the dissociative electron attachment in H2O and D2O: The A1 resonance and axial recoil approximation

N Bhargava Ram, Vaibhav S Prabhudesai and E Krishnakumar ...... 271–279

2 Dynamics of the A1 negative ion resonance in water is probed using velocity – – slice imaging of H from H2O and D from D2O. While the momentum distributions of the highest energy ions agree with quantum calculations, those of low energy ions indicate the role of bending mode excitations before dissociation.

Exploring control parameters of two-photon processes in solutions

Debabrata Goswami and Amit Nag ...... 281–289

We demonstrate how, irrespective of chromophore characteristics, the femtosecond laser pulse repetition rate, chromophore environment and incident laser polarization are effective control parameters for nonlinear optical properties arising from two-photon processes. Normalized Single & Two-Photon Fluorescence 8 Contents

On the nature of highly vibrationally excited states of thiophosgene

Srihari Keshavamurthy ...... 291–300

Dynamical assignment of highly vibrationally excited states of thiophosgene is made using two recent techniques based on classical-quantum correspondence. The analysis give insights into eigenstate sequences and predicts possible bifurcations at energies far above the ground state.

Adsorption of croconate dyes on TiO2 anatase (101) surface: A periodic DFT study to understand the binding of diketo groups

Avinash L Puyad, C H Ramesh Kumar and K Bhanuprakash ...... 301–310

Adsorption of diketo groups of model croconates in bidentate bridging fashion on the TiO2 anatase (101) surface has binding energy of 23.2 kcal/mol and 28.7 kcal/mol which is competitive to the carboxylic acid binding. There is a decrease in charge transfer to the TiO2 due to the biradical nature of the molecules leading to lesser efficiency.

3 10 Quantum dynamics of the Cl+H2 reaction at ultracold

2 Reactive temperatures 10 Non-reactive )

2 1 10 –

cm N Balakrishnan ...... 311 316 0 -16 10

-1 10 Cross sections for non-reactive vibrational quenching leading to Cl+H2(v=0)

-2 and chemical reaction leading to HCl+H channels in Cl+H (v=1,j=0) collisions 10 2 as functions of the incident kinetic energy. -3 10 Cross section (10

-4 10

-5 10 -9 -8 -7 -6 -5 -4 -3 -2 -1 0 10 10 10 10 10 10 10 10 10 10 Incident kinetic energy (eV)

Hydration dynamics of protein molecules in aqueous solution: 1 (a) Backbone oxygen Unity among diversity Sidechain oxygen 0 0.8 Lysozyme

-0.5 0.6 –

(t)>) Biman Jana, Subrata Pal and ...... 317 325 b -1 (0)n 0.4 a Probability -1.5 (1-

10 Bulk This study reveals a bimodal electrostatic energy distribution of protein–water Backbone oxygen 0.2 log -2 Sidechain oxygen hydrogen bonds involving side chain oxygen and faster than bulk water

0 -2.5 02460246810 hydrogen bond breaking dynamics of protein–water hydrogen bond involving -E (k T) time (ps) Electrostatic B backbone oxygen. Contents 9

Potentials of mean force for the exo and endo solvolysis of 2-norbornyl chloride in water and DMSO: A constrained molecular dynamics study Subodh C Tiwari, Timir Hajari, Ashish Sharma and B L Tembe ...... 327–332

The gas phase potential energy curves for the 2- norbornyl chlorides are computed by ab-initio methods and constrained molecular dynamics is used to calculate the potentials of mean force for the exo and endo dissociation of 2- norbornyl chlorides in two solvents, namely water and dimethyl sulfoxide (DMSO).

Cover picture: Theoretically predicted tertiary structure of a protein by Bhageerath software (red), superimposed on experimental structure (blue): PDBID 2V75 (left figure), and three adiabatic electronic potential energy surfaces exhibiting a single point degeneracy for the dynamics study of a three- fold pseudo–Jahn–Teller system (right figure). For details, see B Jayaram et al. (pp. 83–91) and also Biplab Sarkar and A J C Varandas (pp. 115–120).

Indexed in CURRENT CONTENTS ISSN 0974-3626 Edited and published by N Mukunda for the Indian Academy of Sciences, Bangalore 560 080. Printed at Printek Printers, Bangalore 560 079.