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Title: Simplified continuum solvent model with a smooth cavity based on volumetric data

We present a continuum solvent model (CSM) with a smooth cavity for the application in grid-based electronic structure methods. The cavity is identified with the inherently smooth distribution function of a binary mixture at infinite dilution. We obtain a cavity model based on atomic van der Waals radii and one free parameter controlling the overall size. This single parameter is sufficient to adequately reproduce experimental partial molar volumes. The CSM based on this cavity is of similar accuracy in the prediction of aqueous solvation Gibbs energies of small neutral molecules and ions as other CSMs with a smooth cavity. We apply the model to systems in non-aqueous solution, i.e., spiropyran/merocyanin energetics, a proton transfer reaction in dimethyl sulfoxide, and the electrostatic screening of charged gold clusters in an ionic liquid.
Authors:
 [1] ;  [1] ;  [2]
  1. Freiburger Materialforschungszentrum, Albert-Ludwigs-Universität Freiburg, Stefan-Meier-Straße 21, D-79104 Freiburg (Germany)
  2. (Germany)
Publication Date:
OSTI Identifier:
22415310
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 17; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACCURACY; AQUEOUS SOLUTIONS; BINARY MIXTURES; CAVITIES; DILUTION; DISTRIBUTION FUNCTIONS; DMSO; ELECTRONIC STRUCTURE; FORECASTING; GOLD; GRIDS; LIQUIDS; MOLECULES; PARTIAL MOLAL VOLUME; PROTONS; SOLVATION; SOLVENTS; TRANSFER REACTIONS; VAN DER WAALS FORCES