- •Table of Contents
- •Preface
- •Contributors
- •1. INTRODUCTION
- •2. HIERARCHIES OF AB INITIO THEORY
- •2.3. Computational Cost
- •3.2. The CCSD(T) Model
- •4.1. Electronic and Nuclear Contributions
- •4.2. Dependence on the AO Basis Set
- •5.2. Extrapolations from Principal Expansions
- •6. CALIBRATION OF THE EXTRAPOLATION TECHNIQUE
- •6.2. Total Electronic Energy
- •6.3. Core Contributions to AEs
- •7. MOLECULAR VIBRATIONAL CORRECTIONS
- •8. RELATIVISTIC CONTRIBUTIONS
- •9. CALCULATION OF ATOMIZATION ENERGIES
- •10. CONCLUSIONS AND PERSPECTIVES
- •2. STEPS IN THE W1 AND W2 THEORIES, AND THEIR JUSTIFICATION
- •2.1. Reference Geometry
- •2.2. The SCF Component of TAE
- •2.3. The CCSD Valence Correlation Component of TAE
- •2.4. Connected Triple Excitations: the (T) Valence Correlation Component of TAE
- •2.6. Scalar Relativistic Correction
- •3. PERFORMANCE OF W1 AND W2 THEORIES
- •3.2. Electron Affinities (the G2/97 Set)
- •3.4. Heats of Formation (the G2/97 Set)
- •3.5. Proton Affinities
- •4. VARIANTS AND SIMPLIFICATIONS
- •4.2. W1h and W2h Theories
- •4.5. W1c Theory
- •4.6. Detecting Problems
- •5. EXAMPLE APPLICATIONS
- •5.1. Heats of Vaporization of Boron and Silicon
- •5.2. Validating DFT Methods for Transition States: the Walden Inversion
- •5.3. Benzene as a ”Stress Test” of the Method
- •6. CONCLUSIONS AND PROSPECTS
- •1. INTRODUCTION
- •2. THE G3/99 TEST SET
- •4. G3S THEORY
- •5. G3X THEORY
- •6. DENSITY FUNCTIONAL THEORY
- •7. CONCLUDING REMARKS
- •1. INTRODUCTION
- •2. PAIR NATURAL ORBITAL EXTRAPOLATIONS
- •3. CURRENT CBS MODELS
- •4. TRANSITION STATES
- •5. EXPLICIT FUNCTIONS OF THE INTERELECTRON DISTANCE
- •7. NEW DEVELOPMENTS
- •7.1. The SCF Limit
- •7.2. The CBS Limit for the MP2 Correlation Energy
- •7.4. Total Energies
- •8. ENZYME KINETICS AND MECHANISM
- •9. SUMMARY
- •1. INTRODUCTION
- •2. ELECTRON PROPAGATOR CONCEPTS
- •3. AN ECONOMICAL APPROXIMATION: P3
- •4. OTHER DIAGONAL APPROXIMATIONS
- •5. NONDIAGONAL APPROXIMATIONS
- •7. P3 TEST RESULTS
- •7.1. Atomic Ionization Energies
- •7.2. Molecular Species
- •8. CONCLUSIONS AND PROSPECTUS
- •1. INTRODUCTION
- •2. THEORETICAL PROCEDURES
- •3. GEOMETRIES
- •4. HEATS OF FORMATION
- •5. BOND DISSOCIATION ENERGIES
- •6. RADICAL STABILIZATION ENERGIES
- •7. REACTION BARRIERS
- •8. REACTION ENTHALPIES
- •9. CONCLUDING REMARKS
- •1. INTRODUCTION
- •2. HOMOLEPTIC CARBONYL COMPLEXES
- •4. IRON CARBONYL COMPLEXES
- •5. GROUP-10 CARBONYL COMPLEXES
- •7. NOBLE GAS COMPLEXES
- •8. TRANSITION METAL CARBENE AND CARBYNE COMPLEXES
- •12. TRANSITION METAL METHYL AND PHENYL COMPOUNDS
- •13. TRANSITION METAL NITRIDO AND PHOSPHIDO COMPLEXES
- •15. MAIN GROUP COMPLEXES OF BeO
- •16. CONCLUSION
- •1. INTRODUCTION
- •2. THEORETICAL BACKGROUND
- •3. SPECIFIC CONVENTIONS
- •4. STATISTICAL EVALUATIONS
- •5. DISCUSSION
- •Index
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- |
||
|
ities and Chemical Reactivity. 2000 |
ISBN 0-7923-6085-0 |
22. J. Cioslowski (ed.): Quantum-Mechanical Prediction of Thermochemical Data.
2001. ISBN 0-7923-7077-5
Kluwer Academic Publishers – Dordrecht / Boston / London