Theory and Applications of Computational Chemistry / sdarticleindex

Index

phonon operators 378–84, 389–92 phosphane complex bonding 354–7 phosphine bonding 357–60 phosphinidene bonding 332–42 phosphorus 302, 311–14, 357–66 photoactive proteins 269–88 photobiology 269–88

ab initio quantum chemistry 272–6

Aequorea victoria 269–70, 274, 276–9 biomimetic molecular switches 285–7 bovine visual pigments 269, 276–7,

279–85

green fluorescent proteins 269–70, 274, 276–9

luminescent jellyfish 269–70, 274, 276–9 quantum chemistry 272–6

Rhodopsin 269, 276–7, 279–85 photochemistry 269–88

cycloaddition 271–2 funnels 270–1, 660

nickel tetracarbonyl 1099–101, 1120–1 pericyclic reactions 270

reaction paths 274–5 reactivity 659–63

SAC–CI method 1099–101, 1120–1 switching/switches 285–6, 986 valence bond diagrams 659–63

photoelectron spectra 1016–20, 1107–8 photoexcitation 270, 281, 661 photofragmentation reactions 1101, 1120–1 photoisomerization path 277, 282–4 photon energy

exploitation 270, 276–7 wastage 269–70, 274, 276–9

photonic reagents 149–62 photoproducts 270–2, 660 photoprotection/photostability 269 photoreceptors 285 photorhodopsin, photoRh 282–3 phthalocyaninines 1099, 1121–5 physisorption 822–3

Pinchas effect 838 pion-nucleon systems 135 Pipek–Mezey localization 1128

planar unsaturated organic molecules 752–6

plasmon

excitation 49–64 frequencies 49–64

1297

lineshape 52–3

localized surface plasmon resonance 51, 54, 60

oscillations 48–9 resonance 49–64

platinum bonding 332–42 PLEDs 1040–1

PM3 methods

carbon nanostructure self-assembly 879–80

CH· · ·O hydrogen bonds 847 isomeric fullerenes 893

MNDO semiempirical quantum-chemistry 566–76

semiempirical methods 559, 561 unimolecular reaction rates 416 vibrational spectroscopy 166, 179

PMF see potential of mean force Poincare´ surfaces 405–6 Poisson brackets 20

Poisson–Boltzmann equation 44 polarizability

coupled-clusters 133, 1212

dynamic 755, 939, 1101, 1207, 1212 electronic 573, 1028–9, 1031 frequency-dependent 60–1, 1051, 1057–61,

1176, 1182–4 intermolecular forces 1060–2

lithium-hydrogen molecules 628–9 long-range corrections 540 pyridine–copper tetramer 60–3 vibrational 1031

zero frequency 61

Polarizable Continuum Models (PCM) 1184

polarizable potentials 926, 953 polarization

CH· · ·O hydrogen bonds 843, 844 functions 791–2, 795, 800–1, 814 many-body forces 920, 926, 931, 940–2,

956

model 921, 953–7, 1006 molecular Hamiltonians 13

multipole expanded dispersion 1057–8 non-additive interaction energy 940–2 polymer chains 1026–33, 1038 spin-polarization 678–9, 683–5, 777–8,

1134 water 956

1298

polarons 1025 polyacenes 1039

polyacetylenes 1022–3, 1027–32 polyanilines 1025

Po´lya’s enumeration theorem 897 polyatomic molecules 165–90, 251–65 polyatomic monomers 925

polyenes 37, 129–30, 576, 1021, 1039 polyethene chains 1027–8 polyethylene 1013, 1015–20 polyhedr Voronoi 1086

polyhedra 893, 896–7 polymer chains 1011–42

conduction 1020–5 electron transfer 1033–41

electronic properties 1026–33 energy bands/gaps 1013–42 non-linear excitations 1025–33 non-linear optics 1025–33 photoelectron spectra 1016–20 semiconduction 1020–5

polymer coupled-clusters 1213–15 Polymer Light-Emitting Diodes (PLEDs)

1040–1 polymethime chains 1030–2 polymethine dyes 1021 polymethineimine 1030 POLYMODE 253, 254–5 POLYMOL 1012

polynomial expansions 168–9 polyparaphenylenes 1020, 1025, 1034,

1040

polypeptides 285, 963, 965, 987 polyphosphazenes 1030 polyphosphinoboranes 1030 polypropylenes 1019–20 polypyrrole 1020, 1025 polysilacetylenes 1030 polysilane chains 1027–8 polythiophene 1020, 1025 “pop-out” processes 886, 887 Pople and Walmsley misfit 1024 porphyrins 1101, 1121–5 positron annihilation 493 POSMOL 968

post-Hartree–Fock approaches 118, 128, 966

post-transition state dynamics 416–17 potassium 314–22, 980–1

Index

potential energy

coupled-clusters 118–19, 135–6

curves 414–17, 467, 534, 1103–5, 1113, 1120

fullerene formation 878–9 Hartree–Fock functions 109–11

time-dependent molecular theory 16 potential energy surfaces (PES)

anharmonic vibrational spectroscopy 165, 166

beryllium insertion 612, 615–19 boron-hydrogen bond-dissociation 612–13,

624–7

Cope rearrangements 863–5 coupled-cluster theory 118–19, 133, 135–6 electron transfer 1033–41

G3S theory 803 intermolecular forces 1058

lithium-hydrogen 612–13, 619–24, 627–9 many-body perturbation 509

minima 195–218 polyatomic molecules 261–2

reaction pathways 195–202, 230–43 SAC–CI method 1103

size-consistent state-specificity 611, 612–29 time-dependent molecular theory 11–39 transition states 195–202, 218–30 unimolecular reaction rates 409–13 variational transition state theory 67, 80

potential of mean force (PMF) 80 potentials

ab initio 104, 167–8, 173–89, 195–243, 951

curves 118–19, 135–6, 748, 756–60 empirical 176, 188–9, 434, 921, 926–31,

945–6 fitting 174 functions 433–4

n-mode representation 255–60 pairwise-additivity 920, 924–6, 946,

950–7, 1060–2 polynomial expansions 168–9 quartic force fields 180 representations 175–6, 255–60 triple dipoles 923–4

Powell-symmetric-Broyden (PSB) update 220 PPP see Pariser–Parr–Pople predictor-corrector reaction paths 235–6,

242–3

Index

pressure 412–13, 833, 896 product wave functions 15–17 projected frequencies 241–2 projected functions 1052–3 projection operations 472

promotion energy 639, 643, 649–50 promotion gaps 639–48, 658 propagation, Gaussian wave packets 28–9 propagators 120, 430, 443, 453–4, 470–1,

1060–4

protein–ligand interactions 851 proteins 42–5, 104–7, 431

green fluorescent 269–70, 274, 276–9 proton affinity (PA) 794, 797, 802, 805–9 proton donors 831–9

proton transfer 653–4

protonated Schiff bases 274–6, 279, 286 protonation states 44

PS see pseudospectral

PS-VSCF see Partly Separable VSCF PSB see Powell-symmetric-Broyden pseudospectral (PS) approach 545–7 PT see perturbation theory

pulse shaper 149–62

pulsed-field ionization zero-electron-kinetic energy (PFI-ZEKE) 1090–1

punch cards 2–3

push–pull polyene pairs 1029

pyramid particles 51–2, 305, 311, 1111–12 pyridine–copper tetramers 60–3

Q projections 591–8, 607–8

QCAS see quasi-complete active space QCASSCF see quasi-complete active space

self-consistent fields

QCI see quadratic configuration interaction QCPE see Quantum Chemistry Program

Exchange

QDPT see quasi-degenerate perturbation theory

QET see quasi-equilibrium theory QFF see quartic force fields

QM see quantum mechanics

QM/MM see quantum mechanics/molecular mechanics

QST see quadratic synchronous transit quadratic configuration interaction (QCI)

786–7, 791–6, 799–801, 804, 1200 quadratic synchronous transit (QST) 222

1299

quadrupole moments 824, 827 Quantum Chemistry Program Exchange

(QCPE) 3–4

quantum classical Liouville equation 435 quantum coherence 159–60

quantum control mechanism 156–62 quantum dynamic time-dependency 11–12 quantum field theory 120–1, 125–6

lattice 135

quantum fluid mechanics 135

quantum mechanics/molecular mechanics (QM/MM)

GAMESS 1181–4 minimization 203, 209–10 photobiology 275–6, 286

potential energy surfaces 198, 203, 209–10 semiempirical quantum-chemistry 572–4,

576

quantum phenomena controls 149–62 quantum Rice–Ramsperger–Kassel–Marcus

kinetics 413–15 quantum spin 135

quantum vibrational motion of polyatomic molecules 251–65

quantum virial theorem 292–3 quartic force fields (QFF) 180 quasi-classical electrostatic interaction

291–367

quasi-complete active space (QCAS) 588, 610 quasi-complete active space self-consistent

fields (QCASSCF) 514–18 quasi-degeneracy 465, 508–23, 588–9 quasi-degenerate perturbation theory (QDPT)

508–23

quasi-equilibrium theory (QET) 398–420 quasi-fullerenes 898

quasi-Newton methods 204, 206–7 quinone moiety 987–9

quinones 1108–11

r space 486–8, 494–6 R-CCSD(T) 1066

radial distribution functions 1002–3 radicals 187–8, 644–6, 654, 748, 751–6 Raman

reflection 63

spectra/intensity 47, 49, 55–64, 944, 1087, 1176–7

random-phase approximation (RPA) 695, 1207

1300

randomly oriented carbon molecules 883–7 rank

operators 585 reduction 449

rare-gas clusters 921, 924, 945–6 rare-gas crystals 923–4, 944–6 rare–gas molecules 185–6

RAS see restricted active space rate constants 68, 74–5, 79, 82–3

rate-equilibrium relationships 636, 640–2 rational function optimization (RFO) 205–6 Rayleigh–Schro¨dinger perturbation theory

(RSPT) 510–11, 1052–3, 1061–2, 1192–3

RCCSD 1066 reaction

coordinates 75–6, 80–3, 431

paths 79, 195–202, 230–43, 260–5 see also individual reactions

reaction path Hamiltonians (RPH) 230–1, 239, 241, 260–4, 265

reaction-diffusion dynamics 436 reactive empirical bond-orders (REBO)

877–8, 882–3, 886–7 reactive trajectories 69–72

real time non-equilibrium Green Functions 373–95

REBO see reactive empirical bond-orders receptors 965, 980–3

reciprocal form factor 489, 493–5

red shift 831, 837–9, 843–50, 969–71 reduced absorption coefficients 1112–15 reduced density matrices 487–9, 502, 672,

677–9, 726, 727–30

reduced gradient following (RGF) 221 reduced resolvent 940

redundant internal coordinates 213–15, 228–9 reference states 30–2

reference wavefunctions 514–17 refractive index 52–5, 833 rehybridization 838–9, 847 relative free energy 42–3 relative stability 892–3, 896 relativistic

corrections 106 Hamiltonians 548, 550–3 methods 1173–5

molecular theory 507, 540–53 regimes/effects 747–8, 756–60

Index

relativistic scheme by eliminating small components (RESC) 548–9

relaxation energy 1039 reorganization energy 1038, 1039 repulsion 291–367, 840–4, 1053–4

Coulomb 779–80 effects 773–4 integrals 544–5

RESC see relativistic scheme by eliminating small components

resolution of the identity 24, 32, 1082, 1168, 1204–9

resolvent identity 475 resonance

energy 409–13, 652

integrals 129–30, 294, 566–7, 644, 651 states 409–13

theory 117 widths 409–13

response density matrices 1205–6 response functions 133, 374, 445, 455–8 restricted active space (RAS) 588, 761

restricted Hartree–Fock (RHF) 109–11, 789, 864–5

resulting diagrams 123, 127

RFO see rational function optimization RGF see reduced gradient following Rh see Rhodopsin

rhenium bonding 326–32

RHF see restricted Hartree–Fock

Rhodopseudomonas viridis 575–6, 1121, 1124–5

Rhodopsin (Rh) 269, 276–7, 279–85

Rice–Ramsperger–Kassel–Marcus (RRKM) theories 397–420

ridge following methods 223 rigid environments 78 rigid-monomers 1058, 1065

approximation 925 potentials 923–5

rigid-rotor and harmonic-oscillator (RRHO) approximation 893

RIMP2 999

ring diagrams 124–5

Ritz variational principle 118, 125 Roothan–Hall equations 1080 rotational constants 552

rotational spectroscopy 172, 265, 835, 925, 947, 995

Index

rovibrational states/levels 37–8, 409, 627, 944–6, 952, 1065

RPA see random-phase approximation RPH see reaction path Hamiltonians

RRHO see rigid-rotor and harmonic-oscillator RRKM see Rice–Ramsperger–Kassel–Mar-

cus

RSPT see Rayleigh–Schro¨dinger perturbation theory

rubidium bonding 314–22

Runge–Kutta second-order methods 234 ruthenium 347–54, 1116–18, 1157–63 Rydberg excitations 714, 1107, 1126, 1211 Rydberg states 534, 742, 1100

SAC see scaling all correlation

SAC–CI see Symmetry-Adapted Cluster– Configuration Interaction

saddle methods 79, 226–7 SAM1 893

sandwich compounds 320–1, 360–6 SAPT see symmetry-adapted perturbation

theory

satellite spectra 1107–8, 1125–7 saturated pressure 896

SBKJC basis sets 61, 62 scaling

anharmonic vibrational spectroscopy 176–7

electronic structure theory 1168, 1177–81 exchange-correlation 679–80

scale factors 803–7

scaled quantum mechanics (SCM) 167 scaling all correlation (SAC) 803–4 systematic constraint satisfaction 695–6

scanning tunneling microscopy (STM) 373–4

scattering 470–1, 1080–3

optical 47–54, 60, 77, 491–3, 500 SCC see self-correlation correction SCF see self-consistent fields

SCF MO see self-consistent field molecular orbitals

Schellman motif 851 Schrock-type complexes 342–7 Schro¨dinger eigenvalues 11, 15

Schro¨dinger equation 15–17, 117, 196–7, 443–6, 483–5

SCM see scaled quantum mechanics (SCM)

1301

screened hybrids 712–14 seam minimization 210–12

second harmonic generation (SHG) 1026 second order DGE 687–8, 692–3 second order electrical properties 627–9

second order perturbation theory (CASPT2) 518–20, 1065, 1133

Cope rearrangements 864–5, 871 Møller–Plesset (MP2) 744, 820, 825–6,

997, 1172–3

multiconfigurational quantum chemistry 725, 744–8, 754–6, 757, 760–1

photobiology 273–6, 278, 280–3, 286–7 size-consistent state-specificity 586–7

second order reaction path following 234–6 second virial coefficients 833, 926, 952, 1049,

1062 selenium 1118–19

self-consistent field molecular orbitals (SCF MO) 93, 560–2, 570–1, 576, 1051

self-consistent fields (SCF)

convergence 572, 1085–6, 1088–9, 1171 coupled-clusters 117

DFT deMon codes 1085, 1088

Fenske–Hall molecular orbitals 1143–4 GAMESS 1169–72, 1178 intermolecular forces 1051, 1053–4 molecular system simulations 95–103,

109–11

polymer chains 1015–16

semiempirical quantum-chemistry 560–2, 570–1, 576

vibrational 167, 169–72, 174–85, 252–63

self-correlation correction (SCC) 697 self-energies 381–2, 383–4, 389–92 self-exchange charge transfer 1034–5 self-interaction correction (SIC) 531 self-interaction energy 531, 636, 711 self-interaction error 711, 1082 semibullvalene 662–3

semiclassical methods 173 semiconduction 1020–5 semiempirical techniques 559–77

applications 573–6

CNDO 61, 560–3, 568, 834, 1016 INDO 560–3, 567, 569

MINDO 893, 894–5 MINDO/3 calculations 862–3

1302

MNDO 561–70

OM1, OM2 & OM3 567 polymer chains 1016 SINDO1 561, 569, 575

see also AM1; PM3 methods sensors 49, 53–4, 965, 980–3

SERS see surface enhanced Raman spectra SHAKE algorithm 429–30

shake-up effects 134, 1108, 1126, 1210–11 shaped ultra-fast laser pulses 149–62 shell-model 118, 128, 587, 591, 601,

611–12

SHG see second harmonic generation shock compression 435

SIC see self-interaction correction sidewall current flow 813

sigma bonding 778, 783 silicon 654–6

silicon bonding 310, 314–22, 342–7 silicon-containing carbon clusters 521–3 silver 47–64, 347–54, 974–6 SIMOMM 1183

simulated annealing 886–7, 1183 simulations

1930–1960 90–2

carbon nanostructure self-assembly 875–87

DFT 95–103, 108–9 fluid dynamics 105–8

Hartree–Fock 93, 95–104, 106, 109–11 large molecular systems 89–111 MCSCF 95–103, 109–11

self-consistent fields 93, 95–103, 109–11 statistical simulations 105–8

SINDO1 561, 569, 575

single bonds 305–8, 310, 612, 749, 756 single nonpolar bonds 305–7

single reference coupled-clusters (SR CC) 466–8, 474, 582–3

single-reference many-body perturbation theory (SR-MBPT) 509

single-walled carbon nanotubes (SWCNT) 820–3, 875–87

singlet instability 129–30

singlet states 344–5, 376, 773–5, 789 singlet-triplet splitting 513–14

size extensivity 472–6, 1191 iterative corrections 473, 1201

a posteriori correction 469, 476–9, 585

Index

size-consistent state-specific multi-reference (SSMR) methods 581–631

API excitations 582, 587, 593–9, 611–12, 614–15, 617

CAS 583, 586–93, 603, 616

CEPA-like approximations 588–9, 602–5, 612–13, 618–24, 626–7

CMS 587–8, 589–93, 607

Epstein–Nesbet partition 582, 600–2, 612, 615, 625, 627

incomplete model space 581, 584, 606–11 Møller–Plesset partitions 600, 602, 612,

625, 627 performance 611–29

perturbation 587, 599–602, 617–18, 625–7 results 611–29

size-up/size-down mechanisms 875, 887 Slater-type orbitals (STO) 93, 95, 296, 1081 Slater’s exchange term 1079–80

SM see stabilization methods; supermolecular

smoothed particle hydrodynamics (SPH) 437 SN2 reaction 412, 648, 651, 656–7

SO see spin-orbitals SOC 757

sodium bonding 314–22 sodium trimers 948–9

solid–fluid phase transition 426 solid-state optoelectronics 135 solid-state reactions theory 77–83 solitons 1022–5

solvated ions 104–5

solvation 42–4, 81–2, 104–5, 973 equilibrium 80–1 nonequilibrium 81–2

separable equilibrium 80 solvents 77–82, 980–3, 1035–9

GAMESS 1181–5

molecular dynamics development 429–35 non-covalent binding affinity 41–4 plasmon lineshape 52–3

SOS see sum-over-states

space wave functions 484–6, 495–6 space-symmetry broken Hartree–Fock

instabilities 130 SPARTAN 893, 1167 spawning methods 435 species identification 185–6

specific reaction parameters 416, 570, 574–5

Index

spectral shifts 845, 923 spectroscopic constants 624, 625, 759 spectroscopy

absorption spectra 1101, 1111–16, 1120–5 anharmonic vibrational 165–90

electronic 742, 748, 751–6

excitation spectrum 1099, 1100–2, 1106–7, 1111–12, 1116, 1120–4

infrared spectra 189, 263, 831–3, 1062 momentum density determination 493 Raman spectra 47, 59–64, 944, 1087,

1176–7

rotational spectroscopy 172, 835, 925, 947, 995

satellite 1107–8, 1125–7

time domain/resolved 189, 282–4 variational transition state theory 77 vibrational 165–90, 1125–8

X-ray photoelectron 1016–20, 1125 SPH see smoothed particle hydrodynamics spherical particles 48–53, 56–9

spheroid particles 51–3, 170 spin

algebras 123

endohedral fullerenes 983–7 momentum density 489

multiplicity 137, 533, 591, 1101–5, 1129 spin-adaptation 581, 590–2, 605, 619 spin-compensation 684–5

spin-density 728, 753 spin-dependence 123 spin-DFT 677–8, 1082 spin-exchange 776–7 spin-flop EOMCC method 469 spin-functions 1210–11

spin-Hamiltonian mapping 775–7 spin–orbit

corrections 795

coupling 758, 782–3, 1174–5 effect 552, 756

interactions 794, 951

spin-orbitals (SO) 29–32, 726, 728, 731, 758

spin-pairing 644

spin-polarization 678–9, 683–5, 777–8, 1134

spin-scaling 680, 689 spinors 543–4

spiral algorithm 897

1303

spontaneous density fluctuations 374–5, 376–7

SR CC see single reference coupled-clusters SR-MBPT see single-reference many-body

perturbation theory S2RN mechanism 656–8 SRN2c mechanism 656–8

SRPES see synchrotron radiation photoelectron spectra

SS see state-selective/specific SSH see Su, Schrieffer and Heeger

SSMR see size-consistent state-specific multi-reference

stability groups 27

stabilization methods (SM) 458–9 standard free energy of complexation

41–5

state correlation diagrams see valence bond state correlation

state universal (SU) methods 136–9, 583 state-averaged CASSCF 512 state-selective/specific (SS) methods 137 state-specificity 137, 411, 581–631

state–state processes 36–7 static electron correlation 736–8

static polarizability 540, 1027–33 stationary states 9–16, 20, 432, 1208–9 statistical correlation 1001

statistical mechanics 398, 425–32, 793, 901, 1081

statistical simulations 105–8

step-wise mechanisms 413, 475, 638, 646, 652–3, 656–8

stereo conjugated polymers 1027 stereochemical predictions 650–2 steric repulsion 840, 843, 844

STM see scanning tunneling microscopy STO see Slater-type orbitals

stochastic rotation 428, 436 Stokes frequency 56

Stone–Wales transformation 882, 886, 897

stretching frequencies 831, 837–9, 843–50, 969–71

string methods 224, 227, 431 strontium bonding 314–22 SU see state universal

Su, Schrieffer and Heeger (SSH) theory 1023–4

1304

substituent effects 865–71 competitive 866, 869–71 cooperative 865–9

Cope rearrangement 865–70 phenyl 859, 865–6, 871

sulfur 322–6, 1118–19 sum-over-states (SOS) 61, 1212 superconductivity 907 superfluid helium 946

supermolecular (SM) methods 966–7, 1049–56, 1069–72

superoperators 373–95 supramolecular structures 41, 1042 surfaces

chemistry 1167, 1183 hopping 434–5 intersections 210–12 selection rules 61

semiempirical quantum-chemistry 575 surface enhanced Raman spectra (SERS)

49, 55–63

surrounding medium effects 52–3 Suzuki coupling 646

SWCNT see single-walled carbon nanotubes switching/switches, photochemistry 285–6,

986

symmetrized perturbation theory 1051 symmetry dilemma 120, 129–30 Symmetry-Adapted Cluster–Configuration

Interaction (SAC–CI) 1099–137 analytical energy gradients 1102, 1128–9,

1137

bacterial photosynthetic reaction centers 1099, 1101, 1124–5

collision-induced absorption 1099–101, 1112–15

equilibrium geometries 1099–100, 1102, 1128–33

excited states 1099–102, 1105–12, 1115–19, 1122–3, 1128–33

general-R method 920–1, 929–30, 942, 1128, 1129–33

hyperfine splitting constants 1099–100, 1102, 1133–6

ionization spectra 1099–102, 1106–12, 1125–8

method 1102–6

photochemical reactions 1099–101, 1120–1, 1124–5

Index

porphyrins 1101, 1121–5

potential curves 1103–5, 1113, 1120 SD-R method 1102–3, 1132–6 spectra 1107–8, 1112–16, 1122, 1127 transition metals 1099, 1101, 1115–19,

1120–1

van der Waals complexes 1099, 1101, 1112–15

symmetry-adapted perturbation theory (SAPT) DFT 928, 954–7, 1064–5

intermolecular forces 1060–5 many-body forces 919–58 SAPT-5s 935, 951–7

synchrotron radiation photoelectron spectra (SRPES) 1107–8

systematic constraint satisfaction 695–9

tantalum bonding 326–32 tau-dependent functionals 698 Taylor series 234

TD-DFT see time-dependent density functional theory

TDCHF 1060–1

TDHF see time-dependent Hartree–Fock TDVP 24

temperature dependence 135, 412–13, 1003–4 tetrahedra 52–7, 649, 897, 937, 954–5 tetramethylenethane 476

tetraoxo-metal complexes 1116–18 tetraphenyl substituent effects 865–70 thallium bonding 314–22, 332–42 thermal unimolecular dissociation 398 thermochemistry 785–810 thermodynamics

aqueous clusters 968–9 behavior 995–7 carbon clusters 893–6 cycle analysis 42–3 driving forces 861–2

equilibrium 883, 886, 893, 907 intermolecular forces 1058–9 non-covalent binding affinity 42–3 water hexamers 997, 1001

THG see third harmonic generation 1-thiol-4-ethynylphenyl-4’-ethynylphenyl-1’-

benzenethiolate 817–9 thiophene 1106–8

third harmonic generation (THG) 1026 third row elements 807–8

Index

third-order induction 938, 939–42 third-order integrators 236–7

third-order non-linear optical effects 1032–3 Thomas–Fermi model 669, 680, 702, 717,

1080–2

Thomas–Fermi–Dirac model 669, 1080 Thouless determinant 33

three-body forces 943–8

interaction energy 922–38, 944–5, 948–51 potentials 953–4, 957

tight binding deMon DFT 1088

high-temperature quantum chemistry 875–9

molecular conductance 814 nanomaterials 983

one-electron Hamiltonian 766, 776 polymer chains 1024

time evolution 24, 25–9 time-dependent density functional theory

(TD-DFT) 274–5, 530–2, 534–7, 1101

time-dependent Hartree–Fock (TDHF) methods 1052, 1207

time-dependent molecular theory 9–39 coherent states 21–32

Coulombic Hamiltonian 12–17 determinantal coherent states 29–32 direct nonadiabatic dynamics 9–39 dynamic rendering 37–8

electron nuclear dynamics 32–7 Gaussian wave packets 21–9 Hamiltonians 12–17

minimal electron nuclear dynamics 32–7 potential energy surfaces 11–39 quantum mechanics 18–21

time-dependent variational principle 18–21 time-dependent perturbations 120–1 time-dependent Schro¨dinger equation 10–11 time-dependent variational principle 18–21 time-domain experiments 189, 282–4, 399 time-independent perturbation 120–1, 124 time-independent Schro¨dinger equation 196–7 time-resolved spectroscopy 282–4

time’s direction 128

tin bonding 310, 314–22, 342–7

TIP4P water potentials 996, 1002, 1005–6 titanium: sapphire lasers 153

1305

toluene 155 topography 497–8 transition metals

active space selection 741–3 catalysed bond activation 646–7 chemical bonds 291, 294–5, 326–66

designing functional molecular systems 976 dimers 534, 538–40

excitation spectra 1101, 1115–19

Fenske–Hall molecular orbitals 1143, 1144, 1150–63

NMR chemical shifts 1101, 1115–19 orbital ordering 781 photofragmentation 1101, 1120–1 SAC–CI method 1099, 1101, 1115–19,

1120–1

transition probability 157–8 transition states (TS)

assumption 68–72, 76–7, 80–1 barrier heights 517–18

Cope rearrangements 859–72 dividing surfaces 67–81 fundamental dynamical 68, 70, 80–1 hydrogen exchange 527–9 photobiology 270

potential energy surfaces 195–202, 218–30 unimolecular reaction rates 413–14 variational 67–84

transition structures 272, 478, 517 aromatic 860, 862, 864 centauric 860–2

chameleonic 859–60

Cope rearrangement 860–71 stabilization 870

transmission coefficients 82–3 transport

defects 1038 many-body forces 924

molecular dynamics 431–4 molecular wires 374 properties 431, 434, 924 rigid environments 78 solitons 37, 1038

tri-ruthenium dodecacarbonyl 1157–63 triatomic molecules 397–420, 741–2 tricarbonyl-manganate 1143, 1151–6 trideuterium oxide 259–60, 262–3 trimers 922–3, 932–42, 943–57 trimethylamine 101–2

1306

triphenyl substituent effects 865–70 triple dipole terms 923–4

triplet states

electron-electron repulsion 774–7 energy decomposition 345, 363 molecular spectroscopy 1130 multiconfigurational quantum chemistry

732–3 perturbation 476 photobiology 287 valence bonds 645

TRM see trust radius method Trotter factorization 430

truncated tetrahedron particles 55–9 trust radius method (TRM) 205–6 TS see transition states

Tully’s fewest stitches algorithm 434–5 tumor cell lines 477

tungsten 322–32, 342–60 tunneling

electrons 373–95 multi-dimensional 68, 74–5, 82–3 splittings 259–63, 968, 1062

variational transition states 68, 74–5, 82–3 vibration-rotation 947–8, 952, 953–4

twin excitation/transition states 659–63 two-body

cluster expansions 469 interaction energies 932–7 potentials 951–2

two-component relativistic molecular theory 548–53

ubiquinones 1108–9

UEG see uniform electron gas UFF see Universal Force Fields UGA see unitary group approach UHF see unrestricted Hartree–Fock umbrella sampling 430–1 unexpanded dispersion 1054–6

unfilled vacancy molecules 748, 749–51 uniform electron gas (UEG) 670, 679, 682,

684

uniform scaling 679–80

unimolecular dissociation 403–5, 517–18 unimolecular rate constant 400 unimolecular reaction rates 397–420

direct dynamic simulations 415–19 lifetime distribution 400–3

Index

resonance states 409–13 steps 413–15

unitary group approach (UGA) 126 Universal Force Fields (UFF) 820 unlinked diagrams 121–2, 1066, 1193–8 unrestricted Hartree–Fock (UHF) 109–11,

732–3, 789 unsaturated hydrocarbons 794

unsaturated organic molecules 752–6 unsubstituted methane 835–6 updating schemes 204–5, 208–9, 215,

219–20 uracil 832

uranium oxide 741–2

v-representability problems 1082 vacuum

diagrams 121–2 Fermi 468

state 30

valence bond configuration interaction (VBCI) 642–3

valence bond configuration mixing diagrams (VBCMD) 637–8, 652–8

valence bond state correlation diagrams (VBSCD)

applications 642–52 chemical reactivity 637–52

electronic delocalization 658–9 photochemical reactivity 659–63 twin-state concept 659–63

valence bonds (VB) 635–65 CAS 523–9 coupled-cluster theory 117 diagrams 223–4, 635–65

molecular system simulations 91, 101 structures 523, 527–9, 637–43, 652–4,

662–4, 1055 transition states 223–4 wave functions 664–5

valence double zeta (VDZ) 814, 816, 999, 1001

Valence Effective Hamiltonian (VEH) 1016 valence excitation energies 518–21, 755 valence excited state energy 755

valence ionization spectra 1107–8, 1125 valence polarization functions 800–1 valence properties, polymer chains 1016–17 valence states 1100