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Molecular dynamics simulations of liquid methanol and methanol–water mixtures with polarizable models
Author(s) -
Yu Haibo,
Geerke Daan P.,
Liu Haiyan,
van Gunsteren Wilfred F.
Publication year - 2006
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.20429
Subject(s) - polarizability , methanol , chemistry , molecular dynamics , thermodynamics , water model , dielectric , ab initio , ab initio quantum chemistry methods , vaporization , computational chemistry , materials science , molecule , organic chemistry , physics , optoelectronics
A polarizable model for simulation of liquid methanol, compatible with the COS/G2 water model, has been developed using the Charge‐on‐Spring (COS) technique. The model consists of three point charges, with one polarizable center on the oxygen atom. The Lennard–Jones parameters on the oxygen atom together with the molecular polarizability were varied to reproduce the experimental heat of vaporization and density of liquid methanol at ambient conditions. We examined the energies of various methanol dimers in the gas phase and compared them with values obtained from ab initio calculations. The model was then used to study the thermodynamic, dynamic, structural, and dielectric properties of liquid methanol as well as of a methanol–water mixture. A microscopic picture of the structure of pure liquid methanol and of the methanol–water mixture is provided. Good agreement was found between the results from our model simulations and available experimental and ab initio calculation data. In particular, the experimental dielectric permittivity of 32 could be reproduced, which had been shown to be difficult when using nonpolarizable models. © 2006 Wiley Periodicals, Inc. J Comput Chem 27: 1494–1504, 2006