9th Congress on Electronic Structure: Principles and Applications (ESPA 2014): A Conference Selection from Theoretical Chemistry Accounts (Highlights in Theoretical Chemistry (11))

"This volume collects research findings presented at the 9th Edition of the Electronic Structure: Principles and Applications (ESPA-2014) International Conference, held in Badajoz, Spain, on July 2-4, 2014. The contributions cover research work on theory, methods and foundations, materials science, structure and chemical reactivity as well as environmental effects and modelling. Originally published in the journal Theoretical Chemistry Accounts, these outstanding papers are now available in a hardcover print format, as well as a special electronic edition. This volume provides valuable content for all researchers in theoretical chemistry, and will especially benefit those research groups and libraries with limited access to the journal" -- OhioLink Library Catalog Contents 6 Preface to the ESPA-2014 special issue 8 AMOEBA force field parameterization of the azabenzenes 10 1 Introduction 10 2 Computational details 11 2.1 Quantum calculations 11 2.2 Force field 11 2.2.1 The AMOEBA formalism 12 2.2.2 Details of AMOEBA calculations 13 2.3 Parameterization 13 2.4 Atomic multipoles 13 3 Force field validation and refinement of vdW parameters 14 3.1 Bonded interactions, force constants, and vibrational frequencies 14 3.2 Molecular multipoles and electrostatic potential 15 3.3 Intermolecular interactions 15 4 Conclusions 19 5 Supporting information 19 References 19 Triplet–singlet gap in structurally flexible organic diradicals 21 1 Introduction 21 2 Model systems 22 2.1 Computational approach 23 3 Results and discussion 24 3.1 Local minima, isomers and enantiomers 24 3.2 Triplet–singlet gaps 26 4 Conclusions 29 References 29 Separating nuclear spin isomers using a pump–dump laser scheme 31 1 Introduction 31 2 Methods 32 3 Results and discussion 33 3.1 Pump process 34 3.2 Dump process 35 4 Conclusion 37 References 37 Spin delocalization in hydrogen chains described with the spin-partitioned total position-spread tensor 38 1 Introduction 38 2 General formalism: spin partition of TPS tensor 39 3 Computational details 40 4 Results and discussions 41 4.1 Equally spaced hydrogen chains 41 4.2 Dimerized chains 41 4.2.1 Fixed-bond dimerized hydrogen chains 41 4.2.2 Homothetic dimerized hydrogen chains 43 4.3 Asymptotic behavior of the longitudinal position-spread tensors 43 5 Conclusions 44 References 44 Invariant time-dependent exchange perturbation theory and its application to the particles collision problem 46 1 Introduction 46 2 Exchange perturbation theory (EPT), time-dependent perturbation 47 3 Perturbation theory to the first order 49 4 Perturbation theory to the second and higher orders 49 5 S-scattering and T-matrix elements 51 6 Collisions with exchange of electrons 52 7 Scattering of proton by lithium atom with electron exchange 53 8 Conclusions 58 Appendix 1 58 Appendix 2 59 Appendix 3 59 References 61 On the definition of molecular dynamic magnetizability 62 1 Introduction 62 2 Electromagnetic multipole moment operators and the interaction Hamiltonian 64 3 Induced electric dipole moment 65 4 Induced magnetic dipole moment 66 5 Change of response properties and equivalence conditions in a translation of coordinates 67 5.1 Magnitude of origin-shift vectors 67 5.2 Translation of frequency-dependent response tensors 67 6 Variation of frequency-dependent moments in acoordinate translation 69 7 Orders of magnitude 70 8 Concluding remarks 71 References 71 Toward (car)borane-based molecular magnets 73 1 Introduction 73 1.1 The theoretical models 74 1.1.1 Two magnetic sites system 75 1.1.2 Three magnetic sites systems 75 1.1.3 Four magnetic sites system 75 2 Results and discussion 78 3 Concluding remarks 80 References 80 Theoretical analysis of vibrational modes in uranyl aquo chloro complexes 81 1 Introduction 81 2 Computational aspects 82 3 Results and discussion 83 4 Conclusions 87 References 87 Theoretical study of nonlinear optical properties of cobalt bis (dicarbollide) derivatives: the effect of substituents 89 1 Introduction 89 2 Computational procedures 90 3 Results and discussion 90 4 Conclusions 93 References 94 The driving force role of ruthenacyclobutanes 96 1 Introduction 96 2 Computational details 97 3 Results 97 4 Conclusions 100 References 100 Study of electron transport in polybenzenoid chains covalently attached to gold atoms through unsaturated methylene linkers 102 1 Introduction 102 2 Methodology 104 3 Results and discussion 106 3.1 Electric conductance and aromatic stabilization 106 3.2 Electric conductance and occupied–virtual electron promotion 108 4 Conclusions 113 References 113 Revisiting the mechanism and the influence of the excitation wavelength on the surface-enhanced Raman scattering of the pyridine–Ag 20 system 115 1 Introduction 115 2 Computational methods 116 3 Results and discussion 118 3.1 Geometrical optimization and electronic spectra 118 3.2 Static Raman spectra 120 3.3 Resonance Raman spectra 121 4 Conclusions 126 References 126 Effect of van der Waals interactions in the DFT description of self-assembled monolayers of thiols on gold 128 1 Introduction 128 2 Computational details 129 2.1 DFT approach 129 2.2 Slab models 130 3 Results and discussion 130 3.1 Structure of thiol SAMs adsorbed onto the Au(111) surface 130 4 Conclusions 138 References 138 Structural relaxation effects on the lowest 4f−5d transition of Ce3+ in garnets 141 1 Introduction 141 2 Method 142 3 Results and discussion 143 4 Conclusions 148 References 148 A local topological view of pressure-induced polymorphs in SiO 2 150 1 Introduction 150 2 Computational aspects 151 2.1 Total energy and equation of state 151 2.2 Atoms in molecules formalism. Local properties 151 3 Results and discussion 152 3.1 Structure, stability, and equation of state 152 3.2 Chemical bonding. Local properties 153 4 Conclusions 156 References 156 Noncovalent interactions in dimers and trimers of SO 3 and CO 158 1 Introduction 158 2 Computational details 158 3 Results and discussion 159 3.1 Monomers 159 3.2 SO3:CO heterodimers 159 3.3 SO3:(CO)2 heterotrimers 161 3.4 (SO3 )2:CO heterotrimers 163 4 Summary 163 References 164 Is the structure of hydroxide dihydrate OH−(H2O)2 ? An ab initiopath integral molecular dynamics study 166 1 Introduction 166 2 Computational details 167 3 Results and discussion 168 4 Conclusion 170 References 171 Solvation effects on electronic polarization and reactivity indices at the air–water interface: insights from a theoretical study of cyanophenols 172 1 Introduction 172 2 Model 173 3 Results 174 3.1 Energetics, preferred orientations 174 3.2 Reactivity indices 176 4 Discussion and conclusions 176 References 177 Electronic structure of kaempferol–Cu2+ coordination compounds: a DFT, QTAIM and NBO study in the gas phase 179 1 Introduction 179 2 Computational details 180 3 Results and discussion 181 3.1 Molecular structures of kaempferol and its anions 181 3.2 Molecular structure of coordination compounds when the proton is lost 182 3.3 Molecular structure of coordination compounds when the proton is retained 183 3.4 Effects of coordination on the electronic structure of kaempferol and its anions: QTAIM and NBO results 184 4 Conclusions 186 References 187 Scavenger mechanism of methylglyoxal by metformin. A DFT study 189 1 Introduction 189 2 Methodology 190 3 Results and discussion 192 3.1 Condensation of ME and MG 192 3.2 Formation of a zwitterionic triazepine derivative by ring closure 195 3.3 Dehydration 196 3.4 Imine–enamine tautomerism 198 3.5 Enol–keto tautomerism 198 3.6 Hydration of MG 199 4 Concluding remarks 199 References 200 Effects of monohydration on an adenine–thymine base pair 203 1 Introduction 203 2 Methods and computational details 204 3 Results and discussion 205 3.1 Static molecular orbital calculation 205 3.2 Monohydration effect on the hydrogen-bonded structure of adenine–thymine base pair 209 3.2.1 Hydrogen bond between the base pair 209 3.2.2 Hydrogen bond between base pair and watermolecule 210 3.3 Principle component analysis 210 4 Conclusions 212 Appendix 212 References 213 DFT investigation of the formation of linear aminols as the first step toward the induction of oxidatively generated interstrand cross-link DNA lesions 215 1 Introduction 215 2 Methodology 217 3 Results and discussion 217 3.1 Assistance by a water molecule 217 3.2 Assessment of the nucleobases reactivity toward K 218 3.3 The exothermicity as a driving force 220 4 Conclusions 220 References 221 Modeling DNA electronic circular dichroism by QM/MM methods and Frenkel Hamiltonian 222 1 Introduction 222 1.1 Theory 223 1.2 Computational details 224 2 Results and discussion 225 3 Conclusions 227 References 228 Front Matter....Pages i-vi Preface to the ESPA-2014 special issue....Pages 1-2 AMOEBA force field parameterization of the azabenzenes....Pages 3-13 Triplet–singlet gap in structurally flexible organic diradicals....Pages 15-24 Separating nuclear spin isomers using a pump–dump laser scheme....Pages 25-31 Spin delocalization in hydrogen chains described with the spin-partitioned total position-spread tensor....Pages 33-40 Invariant time-dependent exchange perturbation theory and its application to the particles collision problem....Pages 41-56 On the definition of molecular dynamic magnetizability....Pages 57-67 Toward (car)borane-based molecular magnets....Pages 69-76 Theoretical analysis of vibrational modes in uranyl aquo chloro complexes....Pages 77-84 Theoretical study of nonlinear optical properties of cobalt bis (dicarbollide) derivatives: the effect of substituents....Pages 85-91 The driving force role of ruthenacyclobutanes....Pages 93-98 Study of electron transport in polybenzenoid chains covalently attached to gold atoms through unsaturated methylene linkers....Pages 99-111 Revisiting the mechanism and the influence of the excitation wavelength on the surface-enhanced Raman scattering of the pyridine–Ag20 system....Pages 113-125 Effect of van der Waals interactions in the DFT description of self-assembled monolayers of thiols on gold....Pages 127-139 Structural relaxation effects on the lowest 4f−5d transition of Ce3+ in garnets....Pages 141-149 Noncovalent interactions in dimers and trimers of SO3 and CO....Pages 151-158 Is the structure of hydroxide dihydrate OH− (H2O)2? An ab initio path integral molecular dynamics study....Pages 159-166 Solvation effects on electronic polarization and reactivity indices at the air–water interface: insights from a theoretical study of cyanophenols....Pages 167-172 Electronic structure of kaempferol–Cu2+ coordination compounds: a DFT, QTAIM and NBO study in the gas phase....Pages 173-179 Scavenger mechanism of methylglyoxal by metformin. A DFT study....Pages 181-190 Effects of monohydration on an adenine–thymine base pair....Pages 191-204 DFT investigation of the formation of linear aminols as the first step toward the induction of oxidatively generated interstrand cross-link DNA lesions....Pages 205-216 Modeling DNA electronic circular dichroism by QM/MM methods and Frenkel Hamiltonian....Pages 217-223 ....Pages 225-232