- •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
Complete Basis Set Models |
127 |
site of this enzyme. It is hard to imagine a more striking vindication of our assumption that enzymes function by reducing the energies of transition states. The mysterious ways of nature are truly beautiful
[70].
9.SUMMARY
Pair natural orbital extrapolations to the complete basis set limit provide the foundation for a sequence of cost-effective CBS models. The current models: CBS-QCI/APNO, CBS-QB3, and CBS-4M, are applicable to species with 5, 10, and 20 non-hydrogen atoms, and are reliable to ca. 0.5, 1.0, and 2.0 kcal/mol respectively. These methods are applicable to transition states for chemical reactions with the IRCMax procedure. The ZC-VTST CBS-QCI/APNO model is capable of quantitative predictions of absolute rate constants. A double extrapolation promises a new generation of significantly more accurate and reliable models that will no longer require empirical corrections. The isomerasecatalyzed conversion of to provided a case study for the extension of such high-accuracy methods to enzyme kinetics. The impact that high-accuracy computational quantum chemistry is currently having on combustion chemistry will soon be extended to biology. This is an exciting time for computational science.
ACKNOWLEDGEMENTS
The author is grateful to the U. S. Department of Energy and Gaussian, Inc. for the continuing support of this research and recognizes the very important contributions of his many collaborators including: Marc R. Nyden, Mohammad A. Al-Laham, Joseph W. Ochterski, John A. Montgomery, Jr., David K. Malick, Michael J. Frisch, and Rex F. Pratt.
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