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Title: Solute-solvent cavity and bridge functions. I. Varying size of the solute

Abstract

In this work we present the results of the extensive molecular simulations of solute-solvent cavity and bridge functions. The mixtures of Lennard-Jones solvent with Lennard-Jones solute at infinite dilution are considered for different solute-solvent size ratios—up to 4:1. The Percus-Yevick and hypernetted chain closures deviate substantially from simulation results in the investigated temperature and density ranges. We also find that the behavior of the indirect and cavity correlation functions is non-monotonous within the hard-core region, but the latter can be successfully approximated by mean-field theory if the solute-solvent interaction energy is divided into repulsive and attractive contribution, according to Weeks-Chandler-Andersen theory. Furthermore, in spite of the non-monotonous behavior of logarithm of the cavity function and the indirect correlation function, their difference, i.e., the bridge function remains constant within the hard-core region. Such behavior of the bridge and indirect correlation functions at small distances and for small values of indirect correlation function is well known from the Duh-Haymet plots, where the non-unique relationship results in loops of the bridge function vs. indirect correlation function graphs. We show that the same pathological behavior appears also when distance is small and indirect correlation function is large. We further show that the unique functionalmore » behavior of the bridge function can be established when bridge is represented as a function of the renormalized, repulsive indirect correlation function.« less

Authors:
; ;  [1]
  1. Max-Planck Institute for Mathematics in the Sciences, Inselstrasse 22, Leipzig 04103 (Germany)
Publication Date:
OSTI Identifier:
22419805
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 7; 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; DENSITY; DILUTION; INTERACTIONS; MIXTURES; SIMULATION; SOLUTES; SOLVENTS

Citation Formats

Vyalov, I., E-mail: ivan.vyalov@iit.it, Chuev, G., E-mail: genchuev@rambler.ru, and Georgi, N., E-mail: georgi@mis.mpg.de. Solute-solvent cavity and bridge functions. I. Varying size of the solute. United States: N. p., 2014. Web. doi:10.1063/1.4892876.
Vyalov, I., E-mail: ivan.vyalov@iit.it, Chuev, G., E-mail: genchuev@rambler.ru, & Georgi, N., E-mail: georgi@mis.mpg.de. Solute-solvent cavity and bridge functions. I. Varying size of the solute. United States. doi:10.1063/1.4892876.
Vyalov, I., E-mail: ivan.vyalov@iit.it, Chuev, G., E-mail: genchuev@rambler.ru, and Georgi, N., E-mail: georgi@mis.mpg.de. Thu . "Solute-solvent cavity and bridge functions. I. Varying size of the solute". United States. doi:10.1063/1.4892876.
@article{osti_22419805,
title = {Solute-solvent cavity and bridge functions. I. Varying size of the solute},
author = {Vyalov, I., E-mail: ivan.vyalov@iit.it and Chuev, G., E-mail: genchuev@rambler.ru and Georgi, N., E-mail: georgi@mis.mpg.de},
abstractNote = {In this work we present the results of the extensive molecular simulations of solute-solvent cavity and bridge functions. The mixtures of Lennard-Jones solvent with Lennard-Jones solute at infinite dilution are considered for different solute-solvent size ratios—up to 4:1. The Percus-Yevick and hypernetted chain closures deviate substantially from simulation results in the investigated temperature and density ranges. We also find that the behavior of the indirect and cavity correlation functions is non-monotonous within the hard-core region, but the latter can be successfully approximated by mean-field theory if the solute-solvent interaction energy is divided into repulsive and attractive contribution, according to Weeks-Chandler-Andersen theory. Furthermore, in spite of the non-monotonous behavior of logarithm of the cavity function and the indirect correlation function, their difference, i.e., the bridge function remains constant within the hard-core region. Such behavior of the bridge and indirect correlation functions at small distances and for small values of indirect correlation function is well known from the Duh-Haymet plots, where the non-unique relationship results in loops of the bridge function vs. indirect correlation function graphs. We show that the same pathological behavior appears also when distance is small and indirect correlation function is large. We further show that the unique functional behavior of the bridge function can be established when bridge is represented as a function of the renormalized, repulsive indirect correlation function.},
doi = {10.1063/1.4892876},
journal = {Journal of Chemical Physics},
number = 7,
volume = 141,
place = {United States},
year = {Thu Aug 21 00:00:00 EDT 2014},
month = {Thu Aug 21 00:00:00 EDT 2014}
}
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