Open AccessContinuum Electrostatic Behavior of a 3D-RISM Theory
Author(s) -
Benoît Roux
Publication year - 2020
Publication title -
the journal of physical chemistry. b
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.864
H-Index - 392
eISSN - 1520-6106
pISSN - 1520-5207
DOI - 10.1021/acs.jpcb.0c05519
Subject(s) - solvation , isotropy , dielectric , electrostatics , limit (mathematics) , dielectric response , physics , continuum hypothesis , thermodynamics , statistical physics , classical mechanics , quantum mechanics , mathematics , molecule , mathematical analysis
The electrostatic response underlying the 3D-RISM theory and its general relationship to models in which the solvent is represented in terms of a dielectric continuum are examined. It is found that the theory provides a coherent picture of solvation, although its behavior is not entirely consistent with the trends that are expected in the limit of a large solute. The electrostatic discrepancy is due to the nature of the isotropic pair additive site-site correlation function associated with the susceptibility response of the uniform fluid. The influence of the discrepancy in the magnitude of the solvation free energy is negligible for a solvent with a large dielectric constant.