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Extraction of site–site bridge functions and effective pair potentials from simulations of polar molecular liquids
Author(s) -
Chuev Gennady N.,
Vyalov Ivan,
Georgi Nikolaj
Publication year - 2014
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.23586
Subject(s) - polar , bridge (graph theory) , extraction (chemistry) , molecular dynamics , computational chemistry , chemistry , chemical physics , materials science , physics , chromatography , biology , quantum mechanics , anatomy
We develop an efficient method to extract site–site bridge functions from molecular simulations. The method is based on the inverse solution of the reference site interaction model. Using the exact long‐range asymptotics of site–site direct correlation functions defined by the site–site Ornstein–Zernike equations, we regularize the ill‐posed inverse problem, and then calculate site–site bridge functions and effective pair potentials for ambient water, methanol, and ethanol. We have tested the proposed algorithm and checked its performance. Our study has revealed various peculiarities of the site–site bridge functions, such as long‐range behavior, strong dependence on the electrostatic interactions. Using the obtained data, we have calculated thermodynamic properties of the solvents, namely, isothermal compressibility, internal energy, and Kirkwood‐Buff integrals. The obtained values are in excellent agreement not only with molecular simulations but also with available experimental data. Further extensions of the method are discussed. © 2014 Wiley Periodicals, Inc.