Quantum-mechanical Prediction of Thermochemical Data

Quantum-mechanical Prediction of Thermochemical Data......Page 1
Table of Contents......Page 6
Preface......Page 12
Contributors......Page 14
1. INTRODUCTION......Page 16
2.1. The Coupled-Cluster Hierarchy of n-Electron Models......Page 17
2.2. The Correlation-Consistent Hierarchy of One-Electron Basis Sets......Page 19
3.1. Model Calculations on N2 and HF......Page 20
3.2. The CCSD(T) Model......Page 22
4. AN ILLUSTRATIVE EXAMPLE: THE ATOMIZATION ENERGY OF CO......Page 23
4.1. Electronic and Nuclear Contributions......Page 24
4.2. Dependence on the AO Basis Set......Page 26
5.1. Terms Linear in r12......Page 27
5.2. Extrapolations from Principal Expansions......Page 30
6.1. Valence-Shell Correlation Energy......Page 31
6.2. Total Electronic Energy......Page 34
7. MOLECULAR VIBRATIONAL CORRECTIONS......Page 37
8. RELATIVISTIC CONTRIBUTIONS......Page 39
10. CONCLUSIONS AND PERSPECTIVES......Page 40
1. INTRODUCTIONAND BACKGROUND......Page 46
2. STEPS IN THE W1 AND W2 THEORIES, AND THEIR JUSTIFICATION......Page 48
2.1. Reference Geometry......Page 49
2.2. The SCF Component of TAE......Page 50
2.3. The CCSD Valence Correlation Component of TAE......Page 53
2.4. Connected Triple Excitations: the (T) Valence Correlation Component of TAE......Page 54
2.5. The Inner-Shell Correlation Component of TAE......Page 55
2.6. Scalar Relativistic Correction......Page 56
2.7. Spin-Orbit Coupling......Page 57
2.8. The Zero-Point Vibrational Energy......Page 58
3.1. Atomization Energies (the W2-1 Set)......Page 61
3.3. Ionization Potentials (the G2/97 Set)......Page 63
4.1. W1' Theory......Page 65
4.2. W1h and W2h Theories......Page 66
4.3. A Bond-Equivalent Model for Inner-Shell Correlation......Page 67
4.4. Reduced-Cost Approaches to the Scalar Relativistic Correction......Page 69
4.6. Detecting Problems......Page 71
5.1. Heats of Vaporization of Boron and Silicon......Page 72
5.2. Validating DFT Methods for Transition States: the Walden Inversion......Page 73
5.3. Benzene as a ”Stress Test” of the Method......Page 74
6. CONCLUSIONS AND PROSPECTS......Page 76
1. INTRODUCTION......Page 82
2. THE G3/99 TEST SET......Page 84
3. GAUSSIAN-3 THEORY......Page 85
4. G3S THEORY......Page 92
5. G3X THEORY......Page 96
6. DENSITY FUNCTIONAL THEORY......Page 103
7. CONCLUDING REMARKS......Page 109
1. INTRODUCTION......Page 114
2. PAIR NATURAL ORBITAL EXTRAPOLATIONS......Page 115
3. CURRENT CBS MODELS......Page 117
4. TRANSITION STATES......Page 119
5. EXPLICIT FUNCTIONS OF THE INTERELECTRON DISTANCE......Page 124
6. THE cc-pVnZ BASIS SETS......Page 125
7. NEW DEVELOPMENTS......Page 127
7.1. The SCF Limit......Page 128
7.2. The CBS Limit for the MP2 Correlation Energy......Page 129
7.3. The Higher-Order Correlation Energy......Page 132
7.4. Total Energies......Page 133
8. ENZYME KINETICS AND MECHANISM......Page 135
9. SUMMARY......Page 142
1. INTRODUCTION......Page 146
2. ELECTRON PROPAGATOR CONCEPTS......Page 147
3. AN ECONOMICAL APPROXIMATION: P3......Page 149
4. OTHER DIAGONAL APPROXIMATIONS......Page 153
5. NONDIAGONAL APPROXIMATIONS......Page 155
6. AN EXAMPLE OF APPLICATION OF P3: 9-METHYLGUANINE......Page 156
7.1. Atomic Ionization Energies......Page 160
7.2. Molecular Species......Page 166
8. CONCLUSIONS AND PROSPECTUS......Page 170
1. INTRODUCTION......Page 176
2. THEORETICAL PROCEDURES......Page 177
3. GEOMETRIES......Page 182
4. HEATS OF FORMATION......Page 184
5. BOND DISSOCIATION ENERGIES......Page 189
6. RADICAL STABILIZATION ENERGIES......Page 192
7. REACTION BARRIERS......Page 196
8. REACTION ENTHALPIES......Page 206
9. CONCLUDING REMARKS......Page 208
1. INTRODUCTION......Page 214
2. HOMOLEPTIC CARBONYL COMPLEXES......Page 218
3. GROUP-6 CARBONYL COMPLEXES (M = Cr, Mo, W)......Page 221
4. IRON CARBONYL COMPLEXES......Page 222
5. GROUP-10 CARBONYL COMPLEXES......Page 224
7. NOBLE GAS COMPLEXES......Page 225
8. TRANSITION METAL CARBENE AND CARBYNE COMPLEXES......Page 226
9. TRANSITION METAL COMPLEXES WITH LIGANDS......Page 229
10. TRANSITION METAL COMPLEXES WITH GROUP-13 DIYL LIGANDS ER (E = B, Al, Ga, In, Tl)......Page 231
11. TRANSITION METAL COMPOUNDS WITH BORYL LIGANDS AND GALLYL LIGANDS......Page 235
12. TRANSITION METAL METHYL AND PHENYL COMPOUNDS......Page 236
13. TRANSITION METAL NITRIDO AND PHOSPHIDO COMPLEXES......Page 237
14. MAIN GROUP COMPLEXES OF GROUP-13 LEWIS ACIDS......Page 239
15. MAIN GROUP COMPLEXES OF BeO......Page 241
16. CONCLUSION......Page 243
1. INTRODUCTION......Page 250
2. THEORETICAL BACKGROUND......Page 251
3. SPECIFIC CONVENTIONS......Page 252
4. STATISTICAL EVALUATIONS......Page 253
5. DISCUSSION......Page 257
Index......Page 262
References......Page 268