## Quantum-Mechanical Prediction of Thermochemical DataFor 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 |

244 | |

247 | |

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Quantum-Mechanical Prediction of Thermochemical Data Department of Theoretical Chemistry Jerzy Cioslowski No preview available - 2014 |

### Common terms and phrases

accuracy accurate addition applied approach approximation atoms B3LYP barriers basis set BDEs bond calculations CCSD(T Chem chemical Chemistry compared Comparison complexes compounds computational containing contributions convergence corrections correlation correlation energy determined Dunning effects electron electron affinities elements energies error estimate example excitations experiment experimental extrapolation Frenking functions G3 theory G3/99 test set geometries give given Hartree-Fock heats of formation higher important improvement included increase ionization energies J. A. Pople J. M. L. Martin kcal/mol kJ/mol larger less Lett level of theory ligands limit mean absolute deviation methods molecular molecules neutral noted obtained optimized orbitals pairs performance Phys predict present procedure radical Raghavachari reaction reference relative relativistic reliable require respectively scaled similar species Table taken from Ref theoretical thermochemical tion valence values wavefunction

### Popular passages

Page 244 - MJS Dewar and W. Thiel, J. Am. Chem. Soc. 99, 4899 (1977).