Quasi-chemical Theories of Associated Liquids

Abstract

It is shown how traditional development of theories of fluids based upon the concept of physical clustering can be adapted to an alternative local clustering definition. The alternative definition can preserve a detailed valence description of the interactions between a solution species and its near-neighbors, i.e., cooperativity and saturation of coordination for strong association. These clusters remain finite even for condensed phases. The simplest theory to which these developments lead is analogous to quasi-chemical theories of cooperative phenomena. The present quasi-chemical theories require additional consideration of packing issues because they don't impose lattice discretizations on the continuous problem. These quasi-chemical theories do not require pair decomposable interaction potential energy models. Since calculations may be required only for moderately sized clusters, we suggest that these quasi-chemical theories could be implemented with computational tools of current electronic structure theory. This can avoid an intermediate step of approximate force field generation.

20 pages, no figures replacement: minor typographical corrections, four references added, in press Molec. Physics 1998

References in corpus (2)

• Hydrolysis of ferric ion in water and conformational equilibrium
• Critique of Primitive Model Electrolyte Theories

Cited by in corpus (13)

• Combining Machine Learning and Computational Chemistry for Predictive Insights Into Chemical Systems
• Molecular Theory of Hydrophobic Effects: ``She is too mean to have her name repeated.''
• Dielectric continuum methods for quantum chemistry
• Molecular theories and simulation of ions and polar molecules in water
• Tuning ion coordination preferences to enable selective permeation
• Ab initio molecular dynamics calculations of ion hydration free energies
• Ab initio Molecular Dynamics Study of Glycine Intramolecular Proton Transfer in Water
• The hydration state of HO${}^{-}$(aq)
• Balancing Local Order and Long-Ranged Interactions in the Molecular Theory of Liquid Water
• Modeling molecular and ionic absolute solvation free energies with quasi-chemical theory bounds
• Ion-water clusters, bulk medium effects, and ion hydration
• Quadrupole-mediated dielectric response and the charge-asymmetric solvation of ions in water
• Ion Binding Sites and their Representations by Quasichemical Reduced Models