Quantum-Mechanical Prediction of Thermochemical Data

Front Cover
Jerzy Cioslowski
Springer Science & Business Media, Mar 31, 2002 - Science - 256 pages
For the first time in the history of chemical sciences, theoretical predictions have achieved the level of reliability that allows them to - val experimental measurements in accuracy on a routine basis. Only a decade ago, such a statement would be valid only with severe qualifi- tions as high-level quantum-chemical calculations were feasible only for molecules composed of a few atoms. Improvements in both hardware performance and the level of sophistication of electronic structure me- ods have contributed equally to this impressive progress that has taken place only recently. The contemporary chemist interested in predicting thermochemical properties such as the standard enthalpy of formation has at his disposal a wide selection of theoretical approaches, differing in the range of app- cability, computational cost, and the expected accuracy. Ranging from high-level treatments of electron correlation used in conjunction with extrapolative schemes to semiempirical methods, these approaches have well-known advantages and shortcomings that determine their usefulness in studies of particular types of chemical species. The growing number of published computational schemes and their variants, testing sets, and performance statistics often makes it difficult for a scientist not well versed in the language of quantum theory to identify the method most adequate for his research needs.
 

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Contents

Highly Accurate Ab Initio Computation of Thermochemical Data
1
2 Hierarchies of Ab Initio Theory
2
22 The CorrelationConsistent Hierarchy of OneElectron Basis Sets
4
23 Computational Cost
5
32 The CCSDT Model
7
the Atomization Energy of CO
8
41 Electronic and Nuclear Contributions
9
42 Dependence on the AO Basis Set
11
7 New Developments
112
71 The SCF Limit
113
72 The CBS Limit for the MP2 Correlation Energy
114
73 The HigherOrder Correlation Energy
117
74 Total Energies
118
8 Enzyme Kinetics and Mechanism
120
9 Summary
127
Application and Testing of Diagonal Partial ThirdOrder Electron Propagator Approximations
131

5 ShortRange Correlation and the Coulomb Hole
12
52 Extrapolations from Principal Expansions
15
6 Calibration of the Extrapolation Technique
16
62 Total Electronic Energy
19
63 Core Contributions to AEs
22
8 Relativistic Contributions
24
9 Calculation of Atomization Energies
25
References
28
W1 and W2 Theories and Their Variants Thermochemistry in the kJmol Accuracy Range
31
2 Steps in the W1 and W2 Theories and Their Justification
33
21 Reference Geometry
34
22 The SCF Component of TAE
35
23 The CCSD Valence Correlation Component of TAE
38
the T Valence Correlation Component of TAE
39
25 The InnerShell Correlation Component of TAE
40
26 Scalar Relativistic Correction
41
27 SpinOrbit Coupling
42
28 The ZeroPoint Vibrational Energy
43
3 Performance of W1 and W2 theories
46
32 Electron Affinities the G297 Set
48
34 Heats of Formation the G297 Set
50
42 W1h and W2h Theories
51
43 A BondEquivalent Model for InnerShell Correlation
52
44 ReducedCost Approaches to the Scalar Relativistic Correction
54
45 W1c Theory
56
5 Example Applications
57
the Walden Inversion
58
53 Benzene as a Stress Test of the Method
59
6 Conclusions and Prospects
61
References
62
QuantumChemical Methods for Accurate Theoretical Thermochemistry
67
2 The G399 Test Set
69
3 Gaussian3 Theory
70
4 G3S Theory
77
5 G3X Theory
81
6 Density Functional Theory
88
7 Concluding Remarks
94
References
95
Complete Basis Set Models for Chemical Reactivity from the Helium Atom to Enzyme Kinetics
99
2 Pair Natural Orbital Extrapolations
100
3 Current CBS Models
102
4 Transition States
104
5 Explicit Functions of the Interelectron Distance
109
6 The ccpVnZ Basis Sets
110
2 Electron Propagator Concepts
132
P3
134
4 Other Diagonal Approximations
138
5 Nondiagonal Approximations
140
9Methylguanine
141
7 P3 Test Results
145
72 Molecular Species
151
8 Conclusions and Prospectus
155
References
156
Theoretical Thermochemistry of Radicals
161
2 Theoretical Procedures
162
3 Geometrics
167
4 Heats of Formation
169
5 Bond Dissociation Energies
174
6 Radical Stabilization Energies
177
7 Reaction Barriers
181
8 Reaction Enthalpies
191
9 Concluding Remarks
193
References
194
Theoretical Prediction of Bond Dissociation Energies for Transition Metal Compounds and Main Group Complexes with Standard QuantumChemical...
199
2 Homoleptic Carbonyl Complexes
203
3 Group6 Carbonyl Complexes MCO5L M Cr Mo W
206
4 Iron Carbonyl Complexes FeCO4L
207
5 Group10 Carbonyl Complexes MCO3L M Ni Pd Pt
209
6 Group6 Carbonyl Complexes with Phosphane Ligands MCO5PR3 M Cr Mo W R H Me F Cl
210
8 Transition Metal Carbene and Carbyne Complexes
211
9 Transition Metal Complexes with πbonded Ligands
214
10 Transition Metal Complexes with Group13 Diyl Ligands ER E B Al Ga In Tl
216
11 Transition Metal Compounds with Boryl Ligands BR2 and Gallyl Ligands GaR2
220
12 Transition Metal Methyl and Phenyl Compounds
221
13 Transition Metal Nitrido and Phosphido Complexes
222
14 Main Group Complexes of Group13 Lewis Acids EX3 E B Tl X H F Cl
224
15 Main Group Complexes of BeO
226
16 Conclusion
228
References
229
Theoretical Thermochemistry a Brief Survey
235
2 Theoretical Background
236
3 Specific Conventions
237
4 Statistical Evaluations
238
5 Discussion
242
References
244
Index
247
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Page 244 - MJS Dewar and W. Thiel, J. Am. Chem. Soc. 99, 4899 (1977).

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