Theory and Applications of Computational Chemistry / sdarticleindex

Index

valence-Rydberg mixing 746, 1106 valence-universal (VU) methods 136–7, 583 van der Waals

bonding 533–4 clusters 176, 185

collision-induced absorption 1101, 1112–14 complexes 1099, 1101, 1112–15

forces 919, 927–8, 1048 interactions 109, 690, 714, 927, 974 law 1048

molecules 1048, 1064–72

van Vleck perturbation 169, 509, 512 vapor pressure 833

variational principle 12, 18, 32

ab initio vibrational spectroscopy 175 exchange-correlation 674

molecular spectroscopy 1102 multiconfigurational quantum chemistry

733 Ritz 118, 125

variational theory (VT) 137–8, 252–4 variational transition state theory (VTST)

67–84

canonical 69–74, 81–3 condensed phase reactions 77–83 free energy of activation 72, 80–3 gas phase reactions 68–77

quantized dynamical bottlenecks 77, 90 quantized generalized transition state 73–4 rate constants 67–74, 77–83

reaction paths 230–1, 239, 241 solid-state reactions 77–83 thermodynamic formulation 72, 80 variable reaction coordinates 76

VAX 11/780 minicomputer 5 VB see valence bonds

VBCI see valence bond configuration interaction

VBCMD see valence bond configuration mixing diagrams

VBSCD see valence bond state correlation diagrams

VCI see vibrational configuration interaction VDZ see valence double zeta

vector computing architectures 5

VEH see Valence Effective Hamiltonian velocity 237, 427

verifications, transition states 230 Verlet algorithm 226, 427

1307

vertical charge transfer 649–50 vertical electron affinity 443–4, 648–9 vertical excitation energy 754–6

vertical ionization potentials 443–4, 649–50 vertices 121–3, 128, 898

interaction vertices 122–3, 128 supervertices 123

vibration

polyatomic molecules 251–65 polymer chains 1018–19, 1030–3

vibration-rotation-tunneling (VRT) 947–8, 952, 953–4

vibrational analysis 251–2

vibrational configuration interaction (VCI) 254–63

vibrational energy levels 413–14 vibrational frequencies 72–3, 1175–7 vibrational generalized transition state

partition 72–3 vibrational methods

diffusion quantum Monte Carlo 172–3 grid methods 172

harmonic approximation 167–75, 182, 186–7, 252–4, 1030

perturbation theory 168–9 reduced-dimensionality 172 semiclassical methods 173

vibrational modes 60–1, 72–6, 165–80, 262 bending 73, 661–2, 970–1

normal coordinates 251–7, 261–4 normal modes 166–85, 241, 251–64 separability 175

stretching modes/stretching 181–7, 262, 837–40, 968–71

torsion modes/torsions 172–5, 185–7, 260–4

vibrational polarizability 1031

vibrational self-consistent fields (VSCF) 167, 169–72, 174–85, 252–63

correlation-corrected 171, 177–8, 254 DPT2 179

vibrational spectra/spectroscopy 165–90, 1125–8

ab initio 173–87 vibrational transitions 187

combination transitions 186–7 fundamental transitions 167, 187 overtone transitions 186–7

vibrational zero point energy 84, 893, 997

1308

vibrationally adiabatic potentials 74 virial

coefficients 944–5, 1058–9

second 833, 926, 952, 1049, 1062 third 944–5

theorem 292–3, 300 virtual states 253–4 viscosity 833, 1049 visual pigments 276

Vosko–Wilk–Nusair (VWN) correlation 530, 684–5

VRT see vibration-rotation-tunneling VSCF see vibrational self-consistent fields VT see variational theory

VTST see variational transition state theory VU see valence-universal

VWN see Vosko–Wilk–Nusair

water

CH· · ·O hydrogen bonds 833–4, 840–5 clusters

energetics 968–9

finite temperature properties 995–1006 many-body forces 925, 928–42, 947–8,

951–7

Monte Carlo simulations 995–1006 dimers 925, 928–30

hexamers 995–1006

liquid 104, 427–8, 936–7, 954–8, 1001–3 many-body forces 925, 928–42, 947–8,

951–7

molecular dynamics 427–8

molecules 105, 171, 729, 925–38, 969–86 natural orbitals 729–30

non-additive interaction energy 932 potentials 996, 1002, 1005–6 three-body potentials 953–4, 957 trimers 932–42, 947–8, 951–7 vibrational spectra 1127–8

Watson Hamiltonians 171, 252–4 wave functions

coupled-clusters 127–8, 138–9, 470–2 equations of motion 446–7 exchange-correlation holes 701–3 GAMESS 1167–85

intermolecular forces 1052–3

minimal electron nuclear dynamics 32–7 multiconfigurational quantum chemistry

725–61

Index

multireference coupled-clusters 470–2 valence bonds 664–5

wave packets 21–9

weakly bound clusters 976–80 weight factors 127–8 weighted-density approximation 682

Weizsa¨cker kinetic energy density 531, 696–7

Wely groups 23 Wick’s theorem 394–5 width evolution 25–9

Woodward–Hoffmann reactions 646–7 workstations 5–6, 1059

World War II 1079–80

X-ray photoelectron spectroscopy (XPS) 1016–20, 1125

Xa-Scattered Waves (Xa-SW) 1080, 1083–4 xenon hexafluoride 322–6

XPS see X-ray photoelectron spectroscopy

Z-effect 98

Z-matrix coordinates see internal coordinates ZAPT 1178

ZDO see zero differential overlap ZEKE see zero-electron-kinetic energy zero differential overlap (ZDO) 1148 zero frequency polarizability 61 zero-electron-kinetic energy (ZEKE)

1090–1 zero-momentum Hessians 498 zero-point energy (ZPE)

aqueous clusters 968–9 energy decomposition 297

G2 and G3 theories 789–90, 794, 798–800, 803–4

variational transition state theory 72 vibrational configuration interaction 260

zeroth-order approximation 920, 927–8 zeroth-order Hamiltonians 601–2, 745–6 zeroth-order operators 1055–6 zeroth-order regular approximation (ZORA)

548

zeroth-order wave functions 1052–3 Ziegler-Natta reaction 105

zinc bonding 314–22 ZINDO 898

ZORA see zeroth-order regular approximation ZPE see zero-point energy