Index

Averaged coupled-pair functional (ACPF), 42, 44, 54-55, 57 Atomization energy, 2, 6-11, 16, 19, 21-26, 32-34, 37-38, 40, 46-47, 52-53,

55, 58-60, 83, 169, 237

Basis set

3-21G, 104-107, 109, 124, 162

3-21G(*), 102-103

6-31G, 124, 149-150

6-31G(d), 45, 70-71, 73, 76-77, 79, 81-83, 94, 102, 104-107, 109, 122, 151-152, 162, 164-169, 172-173, 175-176, 178-191,

219

6-31G(d,p), 149, 188, 227-228

6-31G(2df,p), 71, 82, 84-87

6-31+G(d), 71

6-311G, 150

6-311G(d,p), 102-103, 107-109, 125, 145, 150, 189 6-311G(2df,2p), 151-152

6-311G(2df,2pd), 227-228 6-311+G(d,p), 181-182, 188-190, 192 6-311+G(2df,p), 124, 175, 179 6-311+G(2df,2pd), 102

6-311+G(3df,2p), 89, 93, 162, 164, 176-178, 180-192 6-311++G, 150

6-311++G(2df,2p), 151-152

6-311++G(3df,3pd), 146-150 Ahlrichs’s, 150, 218 CEP-121G, 150

CEP-31G, 147, 150 CEP-4G, 150

correlation-consistent, 4, 33, 110 aug-cc-pVnZ, 33, 162 aug-cc-pVDZ, 61, 150 aug-cc-pVTZ, 150

247

248 Index

33

cc-pCVnZ, 4-5, 19, 22, 27, 33, 162 cc-pCVDZ, 11, 19-22

cc-pCVTZ, 11, 19, 21-22

cc-pCVQZ, 9, 11, 17, 19, 21, 23, 25, 26 cc-pCV5Z, 11, 19, 21

cc-pCV6Z, 9, 11, 17-21

cc-pVnZ, 4-5, 17-18, 22, 33, 36, 39, 51, 54, 110-117, 119, 162 cc-pVDZ, 6, 8, 17, 39, 110, 113-114, 116-119, 150, 167 cc-pVTZ, 17, 23, 35, 41, 45, 48-49, 60, 113-114, 116-119, 150,

165-169

cc-pVQZ, 17, 60, 83, 113, 117-119, 146-147, 149-150, 155 cc-pV5Z, 7-8, 17, 19, 35, 59-61, 113, 117, 119

cc-pV6Z, 19, 110, 113, 116-117, 119 cc-pVnZ+1, 33

cc-pVTZ+1, 35, 45-47, 57, 164 cc-pVQZ+1, 34-35 cc-pVnZ+2d1f, 33 cc-pV(n+d)Z, 33

cc-pVTZ2P, 45 DZ, 148-150 DZP, 200

Frenking’s II, 200-201, 203-226 G3MP2Large, 73, 164 G3Large, 71-72, 83-84, 87, 164 G3XLarge, 83-84, 87 LANL2DZ, 147-148, 150, 155 LANL2MB, 150 SDB-cc-pVnZ, 61

SHC, 150 Slater-type, 13, 202 TZ, 149-150

TZP, 202-204, 211-212, 216-219, 224-226 TZ2P, 228

TZ(2)P, 210-211

Wachter’s, 150 well-tempered, 146-147, 150

Basis set limit, 11, 16, 36, 61, 67, 99-102, 110, 114-115, 124, 166 Bond dissociation energy (BDE), 161, 174-177, 179, 192, 201-228 Brueckner doubles, 140

249

Complete basis set (CBS) method, 35, 68, 100, 102, 107, 125, 127, 188, 193

CBS-4, 107, 109

CBS-4M, 103, 108, 122, 124, 127 CBS/APNO, 178

CBS-q, 107

CBS-Q, 31, 48, 58, 60, 109, 163-164, 172-173, 178, 188-189 CBS-QB3, 31, 48, 60, 103, 108, 119, 125, 127, 164, 172-173, 178,

181-182, 190 CBS-QCI/APNO, 103, 107-109, 127 CBS-RAD, 164, 172-176, 178-191, 193

Coupled-cluster theory, 3, 99

CCSD, 3-7, 9-11, 17-19, 34, 38-41, 56-57, 60, 101, 107-109 CCSDT, 3, 6, 8, 26, 56, 165

CCSDT-1a, 39

CCSD(T), 7-11, 17, 19-28, 33-35, 38-41, 45, 48-49, 53-54, 56-57, 59-60, 67-68, 77, 99, 103, 109-110, 112, 117-119, 162164, 167-168, 178, 182, 190, 193, 200-201, 203-216, 221-224

CCSDTQ, 6-7

CCSDTQ5, 6

CCSDTQ56, 6 Configuration interaction

CISD, 34

FCI, 5, 13-14, 16, 117

QCISD, 102-103, 164-165, 167-168, 172-173, 178, 182, 190 QCISD(T), 67-68, 71-72, 77-78, 102, 104, 162-164, 178, 182, 190

Density functional, 68-69, 88, 91-92, 95, 162-163, 167, 190, 200-202, 237238, 243

B3LYP, 33-35, 45-49, 54-61, 77, 82, 84-87, 89-95, 102-103, 125, 162-164, 166-167, 169, 173, 176-178, 180-193, 200-201, 203-208, 215, 218, 220, 222-223, 238-239

B3P86, 238 BH&HLYP, 48, 58-59

BLYP, 88-89, 91-92, 95, 162, 178, 182, 190, 238-239

BP86, 200-201, 203-206, 210-212, 216-219, 238-239 HCTH-120, 58

LDA, 88, 90, 95, 238-239 mPW1K, 49, 58, 59 mPW1PW91, 58 SVWN, 88, 238-239

250 Index

Dyson orbital, 133-134, 136, 140, 142-145, 156

Effective core potential (ECP), 145-151, 155, 200, 204, 215, 219 Stuttgart-Dresden, 147-150, 155, 202

Electron affinity, 46, 48-49, 52, 61, 69, 73-74, 80, 86-87, 131, 138-140, 151-155

Electron propagator theory, 131-132, 135, 138-139 2ph-TDA approximation, 140

ADC(3) approximation, 140 NR2 approximation, 140 OVGF approximation, 139

P3 approximation, 134-135, 140-142, 145-156

Energy extrapolation, 15-16, 26, 33-36, 38-39, 48, 50-51, 57, 60-61, 67, 99-102, 110-120, 124-125, 164

Enthalpy of formation, 50-51, 60-61, 69, 70, 73-74, 80-81, 84-91, 93, 161, 168-173, 237-238, 240, 242

Enthalpy of reaction, 99, 109, 119, 161, 190-192

Gaussian-n (Gn) theory G1, 31

G2, 31, 48, 59, 60, 70, 73, 75-76, 88-89, 91-92, 94-95, 163-164, 170-171, 178, 188-189, 238-239

G2(MP2), 76, 188-189 G2(MP2)-RAD, 188-189 G2(MP2,SVP), 163-164, 181-182, 190 G2(MP2,SVP)-RAD, 164, 188-189 G2-RAD(QCISD), 164, 170, 173, 178

G3, 31, 48, 60, 68, 70, 72-78, 81-86, 88-95, 163-164, 171, 173, 178, 181, 238-239

G3//B3LYP, 77

G3(CCSD), 77

G3(MP2), 68, 73-74, 76, 79, 85-86, 92-94, 163-164, 171, 173, 181182, 190

G3(MP2)-RAD, 164, 171, 173, 175-176, 178-179, 182-191, 193 G3(MP2)-RAD(p), 188-189

G3(MP3), 68, 73-74, 76, 79, 85-86, 92-94 G3-RAD, 164, 171, 173

G3S, 68, 77-81, 84, 86-90 G3S(MP2), 79-81 G3S(MP3), 79-81 G3SX, 84, 86-88, 95 G3SX(MP2), 87 G3SX(MP3), 87-88

251

G3X, 68, 77, 81-86, 88-89, 94

G3X(MP2), 85-86

G3X(MP3), 85-86

Hartree-Fock (HF) approximation, 2, 3, 5-6, 9, 11, 14, 16, 18, 33, 3537, 41-42, 50, 54-57, 59-61, 70, 7778, 83, 85, 87, 102-107, 109, 112-114, 118-119, 122, 124-125, 132-137, 140, 147, 151-152, 155-156, 162-165, 178, 181-182, 190, 193, 200

Higher level correction (HLC), 68, 72, 76-79, 81, 83-86, 91-92, 163

Ionization potential, 46, 48-49, 51-52, 61, 69, 73-74, 80, 86-87, 131, 135142, 147-155

IRCMax, 107-109, 125, 127

Koopmans’s theorem, 134-135, 140, 142, 145

Møller-Plesset (MP) perturbation theory, 3, 162

MP2, 54, 71, 73, 76-77, 81-82, 84, 94, 100, 102-107, 109-112, 114-119, 124, 151-152, 162-165, 168, 173-182, 188-190, 193, 200-201, 203-207, 209-210, 213-215, 219, 221-228

MP3, 73, 102, 124, 162

MP4, 68, 71, 73, 78-79, 88, 103, 162-163, 178, 182, 190, 227-228 MP4(SDQ), 103, 119

ONIOM, 120, 122, 125

Polarizable continuum model (PCM), 120, 125

Pole strength, 134, 136, 140, 145, 156

Proton affinity, 46, 61, 69, 74, 80, 86-87

R12 theory, 15-20, 26, 109-112, 115-117

Radical stabilization energy (RSE), 161, 177-180

Reaction barrier height, 99, 107, 109, 124-125, 161, 181-189

Relativistic energy contribution, 23-26, 28, 34, 41-42, 54-55, 59, 61, 67, 166, 200, 202

mass-velocity term, 23-25, 34, 42, 56, 60 one-electron Darwin term, 23-25, 34, 42, 56, 60 spin-orbit term, 23-25, 34, 42, 50, 60, 72, 166 zero-order regular approximation (ZORA), 202

Semiempirical method, 235-243

AM1, 181-182, 190-191, 235-136, 238-242

MINDO/3, 235, 242

252

Index

MNDO, 235-243

MNDOC, 235, 237, 242

MNDO/d, 235-236, 238-239, 241-242

MSINDO, 235-236, 242

OM1, 235-236, 239-241, 243

OM2, 235-236, 239-241, 243

PM3, 235-236, 238-242

SAM1, 235, 242

SAM1d, 242

SINDO1, 235, 242

Test set

G2/97, 48,50, 68-70, 72-82, 84-85, 89, 94-95, 145, 151-152, 154, 238-240

G2-1 subset, 42, 48-51, 56, 69, 73, 82, 90-91 G2-2 subset, 42, 48, 50-51, 56, 69, 82, 90-91

G3/99, 68-69, 73-74, 76, 80-82, 84-92, 94-95 G3-3 subset, 69, 75, 81-82, 89-91

W2-1, 41, 46-47, 50, 52, 54, 56

Weizmann-n (Wn) theory

W1, 31-41, 46-49, 51-52, 57-61, 118

50-51, 163-165, 172, 174-176, 178-179, 181-182, 193 W1aug, 48

W1c, 47, 56, 61 W1ch, 56, 61 W1CAS, 57

W1h, 47, 49, 51-52, 56, 60-61

W2, 31-41, 46-52, 58-59, 61 W2CAS, 57

W2h, 47, 49, 51, 59-61

Zero-point vibrational (ZPV) energy, 9-10, 22-23, 26, 34, 43-46, 60-61, 70, 76, 82-83, 85, 87, 102, 107, 151, 152, 163-164, 166, 178, 182, 188189, 208, 237-238

Understanding Chemical Reactivity

1.Z. Slanina: Contemporary Theory of Chemical Isomerism. 1986

ISBN 90-277-1707-9

2.G. Náray-Szabó, P.R. Surján, J.G. Angyán: Applied Quantum Chemistry. 1987

ISBN 90-277-1901-2

3.V.I. Minkin, L.P. Olekhnovich and Yu. A. Zhdanov: Molecular Design of Tau-

tomeric Compounds.1988

ISBN 90-277-2478-4

4.E.S. Kryachko and E.V. Ludeña: Energy Density Functional Theory of Many-

Electron Systems. 1990

ISBN 0-7923-0641-4

5.P.G. Mezey (ed.): New Developments in Molecular Chirality. 1991

ISBN 0-7923-1021-7

6.F. Ruette (ed.): Quantum Chemistry Approaches to Chemisorption and Het-

erogeneous Catalysis. 1992

ISBN 0-7923-1543-X

7.J.D. Simon (ed.): Ultrafast Dynamics of Chemical Systems. 1994

ISBN 0-7923-2489-7

8.R. Tycko (ed.): Nuclear Magnetic Resonance Probes of Molecular Dynamics.

1994	ISBN 0-7923-2795-0

9.D. Bonchev and O. Mekenyan (eds.): Graph Theoretical Approaches to Chem-

10.	ical Reactivity. 1994	ISBN 0-7923-2837-X
	R. Kapral and K. Showalter (eds.): Chemical Waves and Patterns. 1995
11.		ISBN 0-7923-2899-X
	P. Talkner and P. Hänggi (eds.): New Trends in Kramers’ Reaction Rate The-
12.	ory.1995	ISBN 0-7923-2940-6
	D. Ellis (ed.): Density Functional Theory of Molecules, Clusters, and Solids.
13.	1995	ISBN 0-7923-3083-8
	S.R. Langhoff (ed.): Quantum Mechanical Electronic Structure Calculations
14.	with Chemical Accuracy. 1995	ISBN 0-7923-3264-4
	R. Carbó (ed.): Molecular Similarity and Reactivity: From Quantum Chemical
	to Phenomenological Approaches. 1995	ISBN 0-7923-3309-8

15.B.S. Freiser (ed.): Organometallic Ion Chemistry. 1996 ISBN 0-7923-3478-7

16.D. Heidrich (ed.): The Reaction Path in Chemistry: Current Approaches and

17.	Perspectives. 1995	ISBN 0-7923-3589-9
	O. Tapia and J. Bertrán (eds.): Solvent Effects and Chemical Reactivity. 1996
18.		ISBN 0-7923-3995-9
	J.S. Shiner (ed.): EntropyandEntropyGeneration. Fundamentals and Applic-
19.	ations. 1996	ISBN 0-7923-4128-7
	G. Náray-Szabó and A. Warshel (eds.): Computational Approaches to Bio-
20.	chemical Reactivity. 1997	ISBN 0-7923-4512-6
	C. Sándorfy (ed.): The Role of Rydberg States in Spectroscopy and Photo-
21.	chemistry. Low and High Rydberg States. 1999	ISBN 0-7923-5533-4
	P.G. Mezey and B.E. Robertson (eds.): Electron, Spin and Momentum Dens-
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22. J. Cioslowski (ed.): Quantum-Mechanical Prediction of Thermochemical Data.

2001. ISBN 0-7923-7077-5

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