An advanced continuum medium model for treating solvation effects: Nonlocal electrostatics with a cavity

被引:48
作者
Basilevsky, MV
Parsons, DF
机构
[1] Karpov Institute of Physical Chemistry, Moscow 103064
关键词
D O I
10.1063/1.472193
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The Born-Kirkwood-Onsager (BKO) model of solvation, where a solute molecule is positioned inside a cavity cut into a solvent, which is considered as a dielectric continuum, is studied within the bounds of nonlocal electrostatics. The nonlocal cavity model is explicitly formulated and the corresponding nonlocal Poisson equation is reduced to an integral equation describing the behavior of the charge density induced in the medium. It is found that the presence of a cavity does not create singularities in the total electrostatic potential and its normal derivatives. Such singularities appear only in the local limit and are completely dissipated by nonlocal effects. The Born case of a spherical cavity with a point charge at its centre is investigated in detail. The corresponding one-dimensional integral Poisson equation is solved numerically and values for the solvation energy are determined. Several tests of this approach are presented: (a) We show that our integral equation reduces in the local limit to the chief equation of the local BKO theory. (b) We provide certain approximations which enable us to obtain the solution corresponding to the preceding nonlocal treatment of Dogonadze and Kornyshev (DK). (c) We make a comparison with the results of molecular solvation theory (mean spherical approximation), as applied to the calculation of solvation energies of spherical ions. (C) 1996 American Institute of Physics.
引用
收藏
页码:3734 / 3746
页数:13
相关论文
共 78 条
[51]   REORGANIZATION ENERGY OF ELECTRON-TRANSFER IN POLAR LIQUIDS - DEPENDENCE ON REACTANT SIZE, TEMPERATURE AND PRESSURE [J].
MATYUSHOV, DV .
CHEMICAL PHYSICS, 1993, 174 (02) :199-218
[52]   A MOLECULAR TREATMENT OF SOLVENT EFFECTS ON INTERVALENCE ELECTRON-TRANSFER [J].
MATYUSHOV, DV ;
SCHMID, R .
JOURNAL OF PHYSICAL CHEMISTRY, 1994, 98 (19) :5152-5159
[53]   ELECTROSTATIC INTERACTION OF A SOLUTE WITH A CONTINUUM - A DIRECT UTILIZATION OF ABINITIO MOLECULAR POTENTIALS FOR THE PREVISION OF SOLVENT EFFECTS [J].
MIERTUS, S ;
SCROCCO, E ;
TOMASI, J .
CHEMICAL PHYSICS, 1981, 55 (01) :117-129
[54]  
Mikhlin SG, 1977, Linear Partial Differential Equations
[55]   SIMULATIONS OF SOLVATION DYNAMICS IN SIMPLE POLAR-SOLVENTS [J].
NERIA, E ;
NITZAN, A .
JOURNAL OF CHEMICAL PHYSICS, 1992, 96 (07) :5433-5440
[56]  
Newton RG., 2013, Scattering theory of waves and particles
[57]  
Ovchinnikov A. A., 1969, Zhurnal Eksperimental'noi i Teoreticheskoi Fiziki, V56, P1278
[58]  
OVCHINNIKOVA MY, 1985, KHIM FIZ, V4, P3
[59]   DYNAMICS OF ION SOLVATION IN A STOCKMAYER FLUID [J].
PERERA, L ;
BERKOWITZ, ML .
JOURNAL OF CHEMICAL PHYSICS, 1992, 96 (04) :3092-3101
[60]   STATIC LONGITUDINAL DIELECTRIC FUNCTION OF MODEL MOLECULAR FLUIDS [J].
RAINERI, FO ;
RESAT, H ;
FRIEDMAN, HL .
JOURNAL OF CHEMICAL PHYSICS, 1992, 96 (04) :3068-3084