Water: A Comprehensive Treatise: Volume 6: Recent Advances

ISBN-13: 9781468480207 / Angielski / Miękka / 2012 / 456 str.

Felix Franks

Opis

Since the publication of the previous volumes many new aspects of the physical and life sciences have been developed in which the properties of water play a dominant role. The present volume and its companion, still in preparation, deal with topics that were already mentioned in the preface to Volume 5 as gaining in importance.

Spis treści

1 X-Ray and Neutron Scattering by Aqueous Solutions of Electrolytes.- 1. The Basic Structural Problem.- 1.1. Introduction.- 1.2. The Properties of S?? (k).- 1.3. Termination Errors.- 2. X-Ray Studies.- 2.1. Introduction.- 2.2. A Survey of X-Ray Studies.- 2.3. Future Prospects.- 3. Neutron Studies.- 3.1. Introduction.- 3.2. First-Order Difference Scattering Functions.- 3.3. Placzek Corrections to the First-Order Difference ?M0(k).- 3.4. Experimental Procedures.- 3.5. Second-Order Difference Scattering Functions.- 3.6. Experimental Procedures.- 4. Structural Information Derived from Neutron Studies.- 4.1. Introduction.- 4.2. Cationic Hydration.- 4.3. Anionic Hydration.- 4.4. Cation—Cation Distribution Functions.- 4.5. Anion—Anion Distribution Functions.- 5. Conclusions and Future Prospects.- 2 The Organization and Function of Water in Protein Crystals.- 1. Introduction.- 2. Water—Water and Water—Protein Interactions.- 2.1. Possible Solvent Effects in Proteins.- 2.2. Conventional Wisdom of Protein Hydration.- 3. Crystal Structure Analysis of Proteins and Its Subsequent Refinement.- 3.1. Theory, Data Collection, and Initial Solution of the Structure.- 3.2. Refinement of Structure.- 3.3. Summary: Reliability of Atomic Coordinate Data.- 4. Solvent Information from Crystal Structure Analysis.- 4.1. Information from Protein Coordinates.- 4.2. Direct Location of Water Molecules.- 4.3. Water in the Outer Solvent Region.- 5. Summary: What We Think We Now Know.- 6. Current Work and Future Developments.- 6.1. Experimental Work.- 6.2. Theoretical Work.- 3 Ab Initio Methods and the Study of Molecular Hydration.- 1. Introduction.- 2. Monomeric Water.- 3. The Water Dimer.- 4. Polymers of Water.- 5. Solvated Ion Pairs.- 6. Solvation of Molecules and Ions.- 6.1. The Supermolecule Approach.- 6.2. The Continuum Approach.- 6.3. The Statistical Approach Using Solvation Potentials.- 7. Conclusions.- 4 Mixed Aqueous Solvent Effects on Kinetics and Mechanisms of Organic Reactions.- 1. Introduction.- 2. Mixed Aqueous Solutions.- 2.1. Classification.- 2.2. Solvent Parameters.- 3. Solute—Solvent Interactions in Mixed Aqueous Solutions.- 3.1. Hydrogen Bonding.- 3.2. Hydrophobic Interactions.- 3.3. van der Waals Interactions.- 3.4. Electrostatic Interactions.- 3.5. Treatments of Solution Processes in Aqueous Media.- 4. Mixed Aqueous Solvent Effects and Transition-State Theory.- 4.1. Transition-State Theory.- 4.2. Activation Parameters.- 4.3. Solvent Effects on Initial State and Transition State.- 4.4. Isokinetic Relationships.- 5. Kinetic Solvent Effects on Organic Reactions in Mixed Aqueous Solvents.- 5.1. Introduction.- 5.2. Water-Catalyzed Reactions.- 5.3. Acid- and Base-Catalyzed Reactions.- 5.4. Nucleophilic Displacement Reactions.- 5.5. Miscellaneous Reactions.- 5 Solvent Structure and Hydrophobic Solutions.- 1. Introduction.- 2. Thermodynamics: Formalism and Notation.- 2.1. Definitions.- 2.2. Thermodynamics and Distribution Functions.- 2.3. Remarks on Structure.- 3. Solvent Structure and Solution Thermodynamics: Models.- 3.1. Characterization of Hydrophobic Solutions.- 3.2. Effects of Molecular Properties.- 3.3. Hard-Sphere Mixtures.- 3.4. One-Dimensional Solutions.- 4. Evidence from van der Waals Forces.- 4.1. Many-Body Forces.- 4.2. Temperature-Dependent Forces and Salt Effects.- 5. Effect of Solvent Structure on Long-Range Forces.- 5.1. Solute Interactions via Lifshitz Theory.- 5.2. Planar Interactions via Statistical Mechanics.- 6. Short-Range Solute—Solute Interaction.- 6.1. Hard-Sphere Solvent.- 6.2. Lennard-Jones Solvent.- 6.3. Sticky Hard Spheres.- 6.4. Finite-Size Solutes.- 7. Mean-Field Theory of Solvent Structure.- 8. Conclusion.- 6 Computer Simulation of Water and Aqueous Solutions.- 1. Introduction.- 2. Some Aspects of Statistical Mechanics for Molecular Assemblies.- 3. The Molecular Dynamics Method.- 4. Models of the Water Molecule.- 4.1. The Ben-Naim—Stillinger (BNS) Model.- 4.2. The ST2 Potential.- 4.3. Hartree—Fock Potential.- 4.4. Point Charge Models for Monomers.- 4.5. Central-Force Models.- 5. Potentials for Aqueous Solutions.- 5.1. Solutions of Inert Atoms.- 5.2. Ionic Solutions.- 5.3. Organic Molecules and Water.- 6. Molecular Dynamics Studies of Pure Water.- 6.1. Equilibrium Structure.- 6.2. Kinetic Properties.- 7. Monte Carlo Simulations of Pure Water.- 8. Molecular Dynamics Results for Aqueous Solutions.- 9. Monte Carlo Results for Aqueous Solutions.- References.- Author Index.- Compound Index.