Theory and Applications of Computational Chemistry / sdarticleindex
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Index
absorption bands 48–9
absorption spectrum 1111–16, 1120–3 ACES/ACES2 467, 474, 1167, 1200, 1206 acetaldehyde 414
acetylene 308–9, 347–54, 499, 1132–3 ACGTO–DFT 1088
acidity 833, 836, 839–40, 843 actinides 743–4
activated rate processes 430–1 activation
barriers 788, 803, 1040
energy 72–5, 80–4, 465, 863, 1039–41 enthalpy 477–8, 864–7, 871
active orbitals 513–19, 582–93, 601–6, 729–30, 740–50
active space 740–4
see also complete active space ADF 1086
adiabatic approximation 17, 74
connection 377–8, 530, 675 excitation energy 1130–1 ionization 808
potentials 74, 808 reaction theory 68, 74, 120
adsorbates 49, 56, 59, 78, 1100 adsorption 49, 821
AIDS 44–5
alkali fullerides 983–7
alkali metal clusters 315–16, 319–20, 748, 937, 948–9
alkanes 54, 575, 645, 845–6 alkenes 347–54, 836–7
alkyl radicals 645–6 alkylidenes 342 alkylidynes 342 alkynes 347–54, 836–7
all-valence-electron methods 576 AllChem project 1088, 1089
allowed reactions 646–7, 652, 735, 860, 864, 894
allyl radicals 748, 751–6, 860–1
alternant molecular orbitals (AMO) 120, 129 aluminum 314–22, 332–42, 401–2
AM1 166, 416, 791, 847 Cope rearrangements 862–3 isomeric fullerenes 893
quantum chemical molecular dynamics 877–80
semiempirical quantum-chemistry 561–2, 566–70, 573–6
AMBER 275–6, 278, 280, 283, 286 amino acids 179, 285, 835, 837, 851 amino group conformation 1108–9
2’-amino-4-ethynylphenyl-4’-ethynylphenyl- 5’-nitro-1’-benzenethiolate 818–19
ammonia 216–17
anharmonic vibrational spectroscopy 173, 187
CH· · ·O hydrogen bond 834–5, 837 energy decomposition 311–13 molecular conductance 820, 823–9 molecular system simulation 101–2 polyatomic molecule vibrations 259–60
ammonium cations 980–1
AMO see alternant molecular orbitals
1268
AMPAC program 893 analytes 53
analytic derivatives 200, 570–1, 1082, 1178, 1206
analytical energy derivatives 132–40, 198–203, 214, 1175–6, 1203–5
analytical gradients 1176, 1185, 1191, 1200–8, 1211–15
Angle Resolved UPS (ARUPS) 1018 ANHAR 253
anharmonicity 78–9, 81–2 coupling 135, 171, 186–7 oscillators 135 perturbation theory 168–73 scaling factors 167
vibrational frequencies 178, 181, 183–4, 187 vibrational spectroscopy 165–90 vibrational wavefunctions 170, 174
aniline 1025, 1029, 1106, 1111–12, 1137 anions 460, 971–6, 980–1, 1106–11 anisole proton affinities 808–9 anisotropy 53–4
annealing 886, 968, 1183
annihilation operators 123, 375, 391, 448–9, 453–5
Anonymous Parentage for the Inactive (API) excitations 582, 587, 593–9, 611–12, 614–30
anti-H-bonds 832, 838, 844 antibonding
CH· · ·O hydrogen bond 847–8 electron-electron repulsion 773–83 energy decomposition 323–5, 336 multiconfigurational quantum chemistry
730–5, 749–55 antiferromagnetic spin exchange 776–7 antimony 302, 360–6
antisymmetrization 298–9, 927–8, 1048–52, 1061–2
API see Anonymous Parentage for the Inactive approximate exchange functionals 681–2,
708–14
APW see augmented plane waves aqueous clusters 967–73
argon
crystals 933, 944–5 fluids 433–4
liquid-vapor equilibria 945 trimers 932–7, 943–51
Index
argon-hydrogen 932–7, 946–7, 1062 argon-hydrogen fluoride trimers 932–7,
946–7
argon-nitric oxide trimers 948 argon-oxide trimers 948–51 aromaticity 878–9, 979 arsenic 360–6
artificial intelligence 107 ARUPS see Angle Resolved UPS asymptotic
approximation 938 corrections 530–1, 688–91
expansion 491–2, 931, 939, 1089 series 940
ATM see Axilrod-Teller-Muto potential atomic
charges 570, 1177 ions 741
orbitals 117–18, 458, 749–50, 1147–8 atomization energies 538–40, 698, 707–12,
793–4, 800 atomization heat 895 attraction 291, 293–4, 1048 Au–S bonding 816, 819 Au(111) surfaces 814–15, 817
augmented plane waves (APW) 1079 autocorrelation functions 81, 431 auxiliary functions 1081, 1082, 1085–9
avoided crossings 210–12, 459–60, 583, 617, 630, 637–62
Axilrod-Teller-Muto potential (ATM) 923–4, 931, 943–5, 949
azeotrope formation 833
ß-sheets 837, 851 ß-strands 851 B3LYP
anharmonic vibrational spectroscopy 179–85, 189
carbon nanostructure self-assembly 879–80 CH· · ·O hydrogen bond 841
Cope rearrangements 864–6, 868–71 deMon codes 1085, 1087
DFT 530–40 electrodynamics 61–2
endohedral metallofullerenes 901–6 exchange-correlation 699, 709–11, 715 Fenske–Hall molecular orbitals 1145–7,
1150, 1154–6, 1161–3
Index
G2 and G3 theories 788–91, 798–801, 806–8
GAMESS 1168, 1182 isomeric fullerenes 898–906
molecular conductance 816, 826–7 momentum 501–2
quantum chemical molecular dynamics 879–80
relativistic theory 547, 552 backdonation 326–40, 347–9, 353–63
bacterial photosynthetic reaction centers 1099, 1101, 1121–2, 1124–5
bacteriorhodopsin 276–7, 279–85
Baker–Campbell–Hausdorff (BCH) 23, 474, 596, 598
band gaps 713, 985 band structure 1016–41
conduction 1022–5 electron transfer 1033–41 non-linear optics 1025–33
photoelectron spectra 1016–20 semiconduction 1022–5
barium 314–22 barriers
activation 788, 803, 1040 heights 517–18
transition metal dimers 539 valence bonds 635–52
von Barth–Hedin scheme 677, 685, 697–8, 709–10, 1082
basis functions 199–200, 510, 534, 545 DFT 1081–3, 1089–90
equations of motion 458–60 exchange correlation 726, 746–7, 754 G2 and G3 theories 796, 800 semiempirical methods 569–70
basis set superposition error (BSSE) 534, 823, 1049–51
basis sets
anharmonic vibrational spectroscopy 189 bond functions 296
coupled-clusters 117
G2 and G3 theories 791–2, 795 Gaussian 3, 494, 754, 1083 Gaussian functions 754, 1083 Gaussian-orbital 60, 1083 midbond functions 929
molecular system simulations 93–7, 109 momentum 494–8
1269
optimized 93
polarization function 95, 296, 814 SBKJC 61, 62
water hexamer energetics 1001 bathorhodopsin 282–5
BCH see Baker–Campbell–Hausdorff BD see Brueckner doubles
BDE see bond dissociation enthalpy
Becke exchange functionals 296, 539, 715–16 see also B3LYP
Bell–Evans–Polanyi (BEP) principle 636 benzenes 476–7, 525–6, 814–19 benzoquinone 987–9, 1106, 1108–11 benzynes 476–7
BEP see Bell–Evans–Polanyi Bergman reaction 477–8
beryllium 305–7, 314–22, 478, 612, 615–19 beta sheets and strands 837, 851
bifurcation 242 binding affinity 41–5 binding energy
carbon nanotubes 822–7
CH· · ·O hydrogen bonds 840–3 core-electron 1125–6
energy decomposition 293 exchange-correlation 690 G2 & G3 theories 796 many-body forces 948
molecular conductance 820, 822–7 molecular system simulations 109 momentum 491
Monte Carlo simulations 997–8, 1001–4 oxygen 822–3
temperature dependence 1003–4 water hexamers 998, 1003–4
biological sensors 53–4
biomimetic molecular switches 285–7 biomolecular simulations 431 biomolecules
CH· · ·O hydrogen bonds 834–5 molecular dynamics 425, 431, 435 semiempirical quantum-chemistry 572–6
biphenyl oligomers 1034 bipolarons 1025, 1038 bis(benzene)chromium 360–6 bismuth bonding 302–3 BLB see Extended Brillouin’s
Bloch equations 136–7, 469–74 Brillouin–Wigner 469–70, 472
1270
Bloch’s theorem 1013, 1027 blue moon ensemble method 431
blue shift 280–2, 831, 837–9, 843–50, 970 BLYP 539, 715–16
BO see Born–Oppenheimer Bofill’s updating schemes 205 Bohr model 117
Boltzmann factors 69, 893 Boltzmann-dependent activation 1039 BOMD 1090
bond activation reactions 646–7 bond contraction 838, 844–8, 850 bond directional principle 497 bond dissociation energies 808–9
bond dissociation enthalpy (BDE) 861 bond energy 535–6, 845, 895
decomposition 291–5, 340, 344, 362 G2 and G3 theories 808–9 multiconfigurational quantum chemistry
733, 756, 759 valence bonds 645–6
bond exchange 658–9 bond lengths 551–2
Brillouin–Wigner perturbation 467–8 CH· · ·O hydrogen 836–9, 845, 850 coordinate systems 201
Cope rearrangements 859, 864, 866–7, 870–1
diastatine 552
energy decomposition 296–315, 328, 334, 337, 340, 349–53
exchange-correlation functionals 698, 715 gold 547
non-covalent binding affinity 43 photobiology 283–4
polymer chains 1021–2, 1030 QM/MM optimizations 214 SiC3 521
transition metal dimers 539 unimolecular reaction rates 406
bond strength 645, 833, 882–3, 969 energy decomposition 307–11, 329, 338,
356, 366
bonding analysis 295, 320, 338, 347, 367 bonding models 291–5, 314–15, 322, 347,
362
bonding orbitals 733 borane-fluoro bonding 296–302 Born–Huang products 32–3
Index
Born–Oppenheimer (BO) approximation 196, 1030, 1086, 1174
coupled clusters 117 intermolecular forces 1066–8 momentum 483, 490–1 polymer chains 1030–1 potential energy surfaces 19 simulations 415, 1090
time-dependent molecular theory 17 unimolecular reaction rates 415
boron bonding 305–9, 311–22, 332–42 boron fluoride (BF) 297–302, 311 boron nitride 907
boron-hydrogen 612–13, 624–7 boron-nitrogen 311–14 boron-phosphorous 311–14 boson operators 378–80, 394–5
BOVB see breathing orbital valence bonds bovine visual pigments 269, 276–7, 279–85 BP see Breit–Pauli
bracketing 220–4 Brandow diagrams 123
breathing orbital valence bonds (BOVB) 642–3, 653–4
Breit–Pauli (BP) approximations 548
Breit–Pauli (BP) spin-orbit operators 1174–5 bridges 640–2
Brillouin zones 1013–15 energy bands 1013–14
Brillouin–Wigner
Bloch equations 469–70, 472 coupled-clusters 465–79, 1193 perturbation 465–79
resolvent 465, 472–5 broken-symmetry (BS) states 777 bromine 155, 303–5, 526–9 Brønsted parameters 641–2 Brueckner doubles (BD) 794
BS see broken-symmetry
BSSE see basis set superposition error Buckminsterfullerenes 444, 875–8, 885–7,
892–8, 983–4 see also fullerenes
bulk dielectric constants 50–1 bulk water 969
C-conditions 138–9, 473–6
C–H bond dissociation 808, 861
Index
C–H stretching frequencies 831, 837–9, 843–50
C32, C35, C70 885–6, 892, 895–8
C60 444, 788, 875–8, 885–7, 892–8, 980–4 Ca@C72 898, 901–3
CaFeO3 779–80
calcium 314–22, 779–80, 898, 901–5, 1068–9
calix-4-hydroquinone (CHQ) 984–7 calix[4]quinone-hydroquinone (CQHQ)
985–6
canonical coherent states 23–4 Canonical Van Vleck Perturbation Theory
(CVPT) 169
capping processes 875–7, 880–7 Car–Parrinello
DFT deMon codes 1085, 1086 unimolecular reaction rates 415
Car–Parrinello molecular dynamics (CMPD) 107, 433, 881, 926
carbenes 342–7, 646–7 carbide diatomics 478
carbocylic conjugated systems 981–2
carbohydrate crystals 837 13C NMR 902–3, 905
carbon
bonding 305–10, 314–22, 332–47, 406–7
carbon nanotubes (CNT) 574, 813–14, 820–9, 875–87, 982–3
carbon–carbon bonds 38, 878
Cope rearrangements 859–60, 871 energy decomposition 305–6, 309 lengths 406–7, 755, 871
polymer chains 1017, 1021 strengths 882–3
clusters 883–7, 892, 893–6 energetics 893–6
hyperfine splitting constants 1135 isomers 875–87
monophosphides 314–22, 332–42 nanochemistry 878
nanomaterials 983–7
nanostructures self-assembly 6, 875–87 nanotubes 574, 813–14, 820–9, 875–87,
982–3
nucleophilic substitution 654–6 vapor 896
see also CH· · ·O hydrogen bonds; fullerenes
1271
carbon monoxide
energy decomposition 296–302, 326–32, 357–60
excited states equilibrium geometries 1129–32
Fenske–Hall molecular orbitals 1143, 1151–63
helium interaction 1068–9 molecular dynamics 427 transition metal bonding 326–32
carbonic difluoride 789
carbonyl complex bonding 326–32 carboxy-terminated alkane thioate 54 carbyne complex bonding 342–7 Cartesian coordinates 1056, 1083–5
momentum 428–9, 483–4, 493 polyatomic molecules 261, 264
potential energy surfaces 201–2, 209–14, 228, 231, 241
time-dependent molecular theory 9–14, 25, 33–6
CAS see complete active space Casimir–Polder integrals 1057
CASPT see complete active space perturbation theory
CASPT2 see second order perturbation theory CASSCF see complete active space
self-consistent fields
CASSI see complete active space state interaction
CASVB see complete active space valence bonds
catalytic mechanisms 982–3 catalyzed bond activation 646–7 cations 494, 972–3, 977–81 CBS methods 787
CC see coupled-clusters
CC-LRT see coupled-cluster linear response theory
CCD see coupled-cluster doubles CCSD
ab initio quantum chemistry 1197–202, 1206–7, 1209, 1211–12, 1214 anharmonic vibrational spectroscopy 179
Brillouin–Wigner perturbation theory 465–9, 471–9
CH· · ·O hydrogen bond 840–1 coupled-cluster theory 127, 129–34, 136–8 G2 and G3 theories 786, 791, 794, 799, 808
1272
GAMESS 1170, 1172 intermolecular forces 1063–4
many-body forces 928–9, 935–7, 943, 947
molecular conductance 823, 826 molecular spectroscopy 1130–1 multireference perturbation 520–3
size-consistent state-specificity 583–5, 599, 617
structure stability 521–3 valence bond diagrams 643 water trimers 947–8
CCSD(T)
anharmonic vibrational spectroscopy 179 Brillouin-Wigner perturbation 465–9, 474,
477–8
CH· · ·O hydrogen bond 840–1 coupled-cluster theory 129–34, 137,
1197–202, 1206–14
G2 and G3 theories 786, 791, 794, 799,
808
GAMESS 1170–4, 1180, 1185 intermolecular forces 1063–6 many-body forces 935–7, 943, 947 molecular conductance 823, 826 molecular spectroscopy 1130–1 size-consistent state-specificity 583–4 structure stability 521–3
valence bond diagrams 643
CEBE see core-electron binding energy cellular automata 107
centroid path integral dynamics 435 CEPA see coupled electron pair
approximation Ceperley–Alder data 684–5 cesium bonding 314–22
cesium xenon systems 1101, 1112–15 CF see Coulson–Fischer
CG-DMS see conjugate gradient density matrix search
chair-like transition states 859–61 chameleonic transition states 859–72 charge conductivity 382–4
charge density 130, 298, 483, 658, 977 fitting 1081–2
Hilbert space 387–9 intermolecular forces 1060, 1079 matrices 728, 778
polymer chains 1038
Index
charge distribution 282, 1070–1 DFT 1177, 1181
energy decomposition 296–8, 327, 333, 336–7
many-body forces 932, 941 semiempirical quantum-chemistry 563,
575
charge transfer (CT) aniline 1108–9
CH· · ·O hydrogen bonds 843–4 excitation energies 534–8 polymer chains 1020–5, 1034
states 81, 575, 657, 1020, 1111, 1173 valence bond diagrams 649–50
charged solitons 1023–5 CHARMM 275–6
chemical accuracy 508–9, 785–7, 1085 chemical bonds 527–8
breaking 155
Brillouin–Wigner perturbation 466 configuration interaction 773–4 coupled-cluster theory 118, 133–6 electronic structure changes 730–4 energy decomposition 291–367 fullerenes 877
main-group compounds 291, 294–326 molecular spectroscopy 1125, 1127 molecular system simulations 90, 108,
111 momentum 497
multiconfigurational quantum chemistry 726, 730–3, 743, 749, 756
photonic reagents 149, 155 polymer chains 1035, 1038
transition metal compounds 291, 294–5, 326–66
valence bond diagrams 635 chemical enhancement 59 chemical reactions
allowed 646–7, 652, 735, 860, 864, 894 forbidden 517, 637, 641, 646–7, 652, 735 radicals 187–8, 644–6, 654, 748, 751–6
chemical reactivity 94, 275, 466, 635–65, 1022
chemical sensors 53–4, 820–9, 965, 980–3 chemical shifts
NMR 570–4, 843–5, 1101, 1115–20 transition metal complexes 354, 1101, 1119,
1137
Index
chemisorption 78, 823–4, 1081, 1084 chirality 875, 880, 893, 907
chlorine
CH· · ·O hydrogen bonds 835
energy decomposition 303–5, 311–14, 354–7
fluorides 809
hydrogen exchange 526–9 photonic reagents 155
1-chloro 2-fluorethane 212–13 chloroform 832
CH· · ·O hydrogen bonds 831–52
C–H stretching frequencies 831, 837–9, 843–50
early thinking 832–7
frequency shifts 831, 837–9, 843–50 CHQ see calix-4-hydroquinone chromium 733–5, 740–2
chromium-hydrogen 741–2 dimers 539, 741–2
energy decomposition 347–60 polymer chains 1034–5 tetraoxide 1116–18
chromophores 1099, 1101, 1121–3 chromyl chloride 1115–16
CI see configuration interaction; conical intersections
clamped-nuclei 919–21 classical coherent states 23–4 classical electrodynamics 47–58
classical electrostatic attraction 293–4 classical mechanics 68–72
classical molecular dynamics 428–32 Clebsch–Gordon coupled product 1057 closed operators 609–10
closed-shell
atoms 919, 948, 1047–72 complexes 950 configuration 136, 627
molecules 92, 100, 564, 726, 744, 1048–9 states 582
wave functions 730–1 clusters
alkali metal 315–16, 319–20, 748, 937, 948–9
amplitudes 592–7, 605 equations of motion 455–7 hydrogen-bonded 171, 182–5 interaction energy 942–8
1273
many-body forces 919–58 open-shell 948–51 operators 455–7, 592–7 rare-gases 921, 924, 945–6
size-consistent state-specificity 592–7 surface enhanced Raman Spectra 59–63 van der Waals 176, 185
see also coupled-clusters
CMPD see Car–Parrinello molecular dynamics
CMS see complete model space CNC polyatomic molecules 1132–3
CNDO see complete neglect of diatomic differential overlap
CNT see carbon nanotubes
coarse grained methods/models 435–7, 1175, 1179–80
cobalt ions 1034, 1035
coherence/coherent states 21–32, 37, 159–60 collagen 837
Colle–Salvetti formula 701–4, 1082 collective hydrodynamics 427 collision energy 36
collision-induced absorption 1099–1101, 1112–15
collision-induced infrared spectra 1058–9 COLUMBUS 760
combination mode transitions 186–7 commutators 376–8, 394, 447–8, 453–5,
592–3
complete active space (CAS)
Brillouin–Wigner perturbation 475–6 intermolecular forces 1065–6 multiconfigurational quantum chemistry
725, 739, 744–8 perturbation 512–17
size-consistent state-specificity 583, 586–93, 603, 616, 625–9
valence bonds 524–6 wave functions 725, 744
complete active space perturbation theory (CASPT) 586–7, 1065–6
complete active space self-consistent fields (CASSCF)
Cope rearrangements 862–5 coupled-cluster theory 119 electronic structure 508 GAMESS 1168–70, 1179, 1184 intermolecular forces 1065–6
1274
many-body perturbation 511–14, 522–3 molecular spectroscopy 1101, 1133 molecular system simulations 101 multiconfigurational quantum chemistry
725, 729–30, 739–48, 754–7, 760–1 multireference perturbation 508–14 photobiology 273–6, 278–83, 286–7 size-consistent state-specificity 584, 613,
616, 625, 628
state interactions 748, 757 valence bonds 523–9 water molecules 729–30 wave functions 739–44
complete active space state interaction (CASSI) method 748, 757
complete active space valence bonds (CASVB) 523–9
complete intermolecular potential surfaces 1047–72
complete model space (CMS) 136–8, 471–8, 587–93, 606–10
complete multi-configurational SCF 101 complete neglect of diatomic differential
overlap (CNDO) 61, 560–3, 568, 834, 1016
complex spectra elucidation 186 complex spin unrestricted Thoulles
determinant 33 complexes
acetylene 342–7, 349, 353–4 carbene 342–7
carbonyl 326–32 carbyne 342–7 dihydrogen 357–60 diyl 332–42, 358 ethylene 349, 353–4 Fischer 342–7 octahedral 322, 329
phosphane 313–14, 347–57, 360 Schrock 342–7
compressed coupled-clusters 1215 Compton
profiles 489, 492–5, 499–500 scattering 491–3
computational electrodynamics 47–64 discrete dipole approximations 47, 50, 60 finite difference time domain 47, 50, 61 multiple multipole method 50
computer experiments 437, 1018–19, 1022
Index
concerted mechanisms 646, 862–3, 871 condensed phases 77–83, 153, 430, 919–58 conductance/conduction 48–53, 373–95,
813–29, 937, 1020–5 configuration interaction (CI)
ab initio quantum chemistry 1195–6, 1203 anharmonic vibrational spectroscopy
170–1, 180
coupled-clusters 118–20, 129, 137–8, 1195–6, 1203
direct 739
electron-electron repulsion 773–4 expansions 739
full 611, 614–15, 727, 1168–72, 1174 GAMESS 1168–74
intermolecular forces 1051, 1055, 1066 large-scale 132, 479, 571, 739, 761, 1213 molecular system simulations 98–9 perturbation selection 587
polyatomic molecules 254–63
quadratic 611, 614–15, 727, 1168–72, 1174 singles 61, 200, 561, 1173–4 size-consistent state-specificity 587 valence bond diagrams 642–3
vibrational 254–63
see also multi-reference-configuration interaction; Symmetry-Adapted Cluster–CI
configuration mixing diagrams 637–8, 652–8 configuration state functions (CSF) 515–17,
524, 1172
multiconfigurational quantum chemistry 727, 734, 739–45
size-consistent state-specificity 586–93, 598, 602, 613–16, 619
configurational heat capacity 1000, 1004 configurations, cyclic 934–5 conformational changes 42–5, 285–7, 419,
431, 1018–19
conical intersections (CI) 210–12, 270–2, 275–6, 282–3, 659–62, 742, 1176–8
conjugate gradient density matrix search (CG-DMS) 572
conjugated organic molecules 1101–2, 1106–12
excitation 1101, 1106–12 ionization 1101, 1106–12 spectra 1101, 1106–12
conjugated polymers 1034
Index
connected cluster theorem 121–3 connected diagrams 121–2, 473–5 connectivity 598–9
constrained ensembles 430 constraint satisfaction 681, 688–99 continuum solvent models 1184 continuum treatments 43–4 control fields 150–62
control landscapes 157–8 coordinates
anharmonic vibrational spectroscopy 170–9
molecular Hamiltonians 11–16
potential energy surfaces 201–2, 209–31 scaling 679–80
variational transition states 68–83 coordination shells 954–6
Cope rearrangements 859–72 AMI calculations 862–3
bond making/breaking 860–4, 871 calculations 859–72
dynamic electron correlation 863–5 interallylic distances 860, 863, 865–7, 869,
871
kinetic isotope effects 862, 865, 871 MINDO/3 calculations 862–3 substituent effects 859, 865–71
copper bonding 347–54 copper tetramers 60–1
copper–pyridine complex 60–3 core states 1100, 1125–8
core-electron binding energy (CEBE) 1125–6 core-ionization spectra 1125
core-valence correlation 795 correction schemes
asymptotic corrections 530–1, 688–91 DFT 507–8, 529–40
electron correlation 1134 exchange-correlation 690–1, 697
G2 and G3 theories 787, 791–2, 795–804 intermolecular forces 1066 orthogonalization 566–7
correlation
ab initio quantum chemistry 1204, 1206 correlation-corrected VSCF 171–2,
174–80, 181–5 coupled-clusters 130, 1204, 1206 DFT 507, 669–717
electrons 5, 118, 124, 730, 736–8, 1134
1275
energy
density-gradient expansions 687 molecular system simulations 94–9,
106–7
multiconfigurational quantum chemistry 736–8
scaling 803–7 G3 theory 795–6
holes see exchange-correlation holes lengths 701, 704
local density approximations 684–6 potentials 501, 703, 714–15, 761
see also exchange-correlation wavefunctions 701–3, 1168
corresponding states law 1048 Coulomb
forces 427–8 holes 99, 736, 738 integrals 1089
interactions 78, 493, 563, 712–14, 1047, 1054, 1181
plasmas 135 repulsion 779–80 screening 712–14 terms 1148
Coulombic Hamiltonian 12–17 Coulombic systems 679
Coulson–Fischer (CF) orbitals 731–3 counterintuitive orbitals 770–2 counterions 280–2
counterpoise method 534, 833–41, 922, 1087 corrections 833–5, 932, 1050, 1054
coupled electron pair approximation (CEPA) ab initio quantum chemistry 1195–7 size-consistent state-specificity 582–3,
587–9, 592–3, 602–5, 610–15, 618–30
coupled-cluster doubles (CCD)
ab initio quantum chemistry 1195–202, 1206
intermolecular forces 1053, 1063 theory 119, 125–34, 1195–202, 1206
coupled-cluster linear response theory (CC-LRT) 1101, 1207, 1212
coupled-clusters (CC) amplitudes 1063
Brillouin-Wigner perturbation 472–6 equations of motion methods 456–60 internal 138
1276
size-consistent state-specificity 586–605 theory 125–39, 1214–15
ansatz 174–5, 468–9, 472, 1063, 1194, 1209, 1213
Brillouin–Wigner perturbation 465–79, 1193
expansion 124, 131–3, 466–8, 585, 1100–2 extended 135
externally corrected 137, 468–9 functionals 1205–7
G2 and G3 theories 786–7, 791, 794 GAMESS 1172–3
intermolecular forces 1063–4 linear 125, 1197
many-body perturbation 119–20, 122–8, 133, 1193–7
multi-reference 135–9, 465–79 state specific 581–631
state universal 468, 474, 585–6 state-selective 137
valence universal 136, 1213 origins 115–40
quantum chemistry 1191–216 SAC–CI method 1101
single-reference 466–77, 582, 602–3, 1192, 1201–2, 1210–12
size-consistent state-specificity 581–631 theory 115–40, 1191–216
coupled-pair many-electron theory (CPMET) 131–2, 1195
coupled-perturbed (CP)-MOD equations 1105 coupling constants 129–37, 509, 673, 753,
1087–8, 1212
coupling matrix elements 241–2 covalent bonds 293–366, 525–9, 644–6,
652–3, 731, 837 covariance functions 1000, 1005 Cp2Ni2 1143, 1151–6
CPHF coefficients 1104
CPMET see coupled-pair many-electron theory
CR-CCSD(T) 134, 1173
R-CCSD(T) 1066
creation operators 30, 123, 375, 391, 446–9, 453–5
critical phenomena 135, 427 cross sections 36–7 crossing point heights 642–3
crossing resonance energy 643
Index
crystal-vapor interfaces 78 crystals 78
argon 933, 944–5
cohesion energy 943–5, 1059 rare-gas 923–4, 944–6 vacancies 945–6
CSF see configuration state functions CT see charge transfer
current, density 387–9, 678
current-voltage (I–V) curves 813–19, 827–8, 1111
curve crossing 637 curvilinear coordinates 76 cusps 736–7, 1134–6
CVPT see Canonical Van Vleck Perturbation Theory
CVT rate constants 74–5 cyclic configurations 934–5 cyclic polyenes theory 130
cycloadditions 271, 635, 646–7, 882 cyclobutadiene 478, 659 cyclobutane 271 cyclohexane-1,4-diyl 212, 860–9 cyclophane systems 988–9
DALTON package 760
damped gradient corrections 690–1 damping constants 60
Datacraft 6024 minicomputers 4 Davidson correction 1066
DC see Dirac–Coulomb
DCB see Dirac–Coulomb–Breit DCD see Dewar–Chatt–Duncanson
DDA see discrete dipole approximation DDI see distributed data interface defect transport 1038
degeneracy
anharmonic vibrational spectroscopy 179–80
chair Cope rearrangements 859–61 molecular system simulations 98–9, 101 multiconfigurational quantum chemistry
734–8
multireference coupled-clusters 465 open-shell monomers 1065–6 perturbation 179–80, 769–70 SAC–CI method 1105
degrees of freedom 14–17, 37–8, 196–7, 1202–7