Molecular Theory of Solvation

ISBN-13: 9789048164004 / Angielski / Miękka / 2010 / 358 str.

F. Hirata

Opis

Molecular Theory of Solvation presents the recent progress in the statistical mechanics of molecular liquids applied to the most intriguing problems in chemistry today, including chemical reactions, conformational stability of biomolecules, ion hydration, and electrode-solution interface. The continuum model of "solvation" has played a dominant role in describing chemical processes in solution during the last century. This book discards and replaces it completely with molecular theory taking proper account of chemical specificity of solvent. The main machinery employed here is the reference-interaction-site-model (RISM) theory, which is combined with other tools in theoretical chemistry and physics: the ab initio and density functional theories in quantum chemistry, the generalized Langevin theory, and the molecular simulation techniques. This book will be of benefit to graduate students and industrial scientists who are struggling to find a better way of accounting and/or predicting "solvation" properties.

Spis treści

Preface. -1: Theory of molecular liquids; F. Hirata. 1. Introduction. 2. Density Fluctuation in Liquids. 3. Ornstein-Zernike (OZ) Equations. 4. Site-SiteOZ (RISM) Equations. 5. Solute-Solvent System. 6. Some applications of RISM Theory. References. -2: Electronic Structure and Chemical Reaction in Solution; H. Sato. 1. Introduction. 2. ab initio Molecular Orbital Theory and the Solvation Effect. 3. RISM-SCF/MCSCF Theory. 4. Acid-base Equilibria in Aqueous Solution. 5. Solvent Effects on Conformational Change of Chemical Compounds. 6. Solvent Effect on Chemical Reactions. 7. The NMR Chemical Shift. 8. Summary. Appendix: 1. Partial Charge Treatment in RISM-SCF/MCSCF. 2. Variational Principle in the RISM-SCF/MCSCF Method. References. -3: Conformational stability of biomolecules in solution; M. Kinoshita. 1. Combined RISM-MC approach for predicting peptide conformations. 2. Alcohol effects on peptide conformations. 3. Salt effects on solvation properties of peptides. 4. Partial molar volume of amino acids and pressure effects. Appendix: 1. Algorithms for solving RISM equations. References. -4: Three-dimensional RISM theory; A. Kovalenko. 1. Introduction. 2. 3D-RISM integral equation. 3. Closures for the 3D-RISM theory. 4. Hydrophobic hydration. 5. Potential of mean force between molecular species in solution. 6. Solvation chemical potential of an ionic cluster in electrolyte solution. 7. Self-consistent 3D-RISM approach. 8. Combined Kohn-Sham DFT and 3D-RISM approach for a metal-liquid interface. 9. Hybrid 3D-RISM-SCF and ab initio MO method for solvated molecules. Appendix: 1. Free energy functions in the KH approximation. 2. Solvation chemical potential in the SC-3D-RISM approach. 3. Solvent effective potential coupling the KS-DFT and 3D-RISM equations. 4. Algorithms for solving the RISM equation. References. -5: Dynamical processes in solution; Song-Ho Chong. 1. Introductory remarks on the theory for dynamics of simple liquids. 2. Interaction-site-model description of molecular-liquid dynamics. 3. Collective excitations in diatomic liquids. 4. Ion dynamics in diatomic liquids. 5. Collective excitations and dynamics of ions in water. 6. Concluding remarks. References.