Quasi-chemical theory with a soft cutoff

Abstract

In view of the wide success of molecular quasi-chemical theory of liquids, this paper develops the soft-cutoff version of that theory. This development has important practical consequences in the common cases that the packing contribution dominates the solvation free energy of realistically-modeled molecules because treatment of hard-core interactions usually requires special purpose simulation methods. In contrast, treatment of smooth repulsive interactions is typically straightforward on the basis of widely available software. This development also shows how fluids composed of molecules with smooth repulsive interactions can be treated analogously to the molecular-field theory of the hard-sphere fluid. In the treatment of liquid water, quasi-chemical theory with soft-cutoff conditioning doesn't change the fundamental convergence characteristics of the theory using hard-cutoff conditioning. In fact, hard cutoffs are found here to work better than softer ones.

5 pages, 2 figures

References in corpus (5)

• Molecular Theory of Hydrophobic Effects: ``She is too mean to have her name repeated.''
• Temperature Dependence of the Hydrophobic Hydration and Interaction of Simple Solutes: An Examination of Five Popular Water Models
• Role of attractive methane-water interactions in the potential of mean force between methane molecules in water
• Balancing Local Order and Long-Ranged Interactions in the Molecular Theory of Liquid Water
• Self Consistent Molecular Field Theory for Packing in Classical Liquids

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• Concentration dependence of the Flory-Huggins interaction parameter in aqueous solutions of capped PEO chains