Polarizable empirical force field for aromatic compounds based on the classical drude oscillator.

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TitlePolarizable empirical force field for aromatic compounds based on the classical drude oscillator.
Publication TypeJournal Article
Year of Publication2007
AuthorsLopes, PEM, Lamoureux, G, Roux, B, Mackerell, AD
JournalJ Phys Chem B
Volume111
Issue11
Pagination2873-85
Date Published2007 Mar 22
ISSN1520-6106
KeywordsBenzene, Dimerization, Models, Chemical, Models, Molecular, Molecular Conformation, Quantum Theory, Solubility, Solutions, Static Electricity, Temperature, Toluene
Abstract

The polarizable empirical CHARMM force field based on the classical Drude oscillator has been extended to the aromatic compounds benzene and toluene. Parameters were optimized for benzene and then transferred directly to toluene, with parameters for the methyl moiety of toluene taken from the previously published work on the alkanes. Optimization of all parameters was performed against an extensive set of quantum mechanical and experimental data. Ab initio data was used for determination of the electrostatic parameters, for the vibrational analysis, and in the optimization of the relative magnitudes of the Lennard-Jones parameters. The absolute values of the Lennard-Jones parameters were determined by comparing computed and experimental heats of vaporization, molecular volumes, free energies of hydration, and dielectric constants. The newly developed parameter set was extensively tested against additional experimental data such as diffusion constants, heat capacities at constant pressure, and isothermal compressibilities including data as a function of temperature. Moreover, the structures of liquid benzene, liquid toluene, and solutions of each in water were studied. In the case of benzene, the computed and experimental total distribution function were compared, with the developed model shown to be in excellent agreement with experiment.

DOI10.1021/jp0663614
Alternate JournalJ Phys Chem B
PubMed ID17388420
PubMed Central IDPMC2519011
Grant ListR01 GM072558 / GM / NIGMS NIH HHS / United States
GM72558 / GM / NIGMS NIH HHS / United States
GM51501 / GM / NIGMS NIH HHS / United States
R01 GM051501-11 / GM / NIGMS NIH HHS / United States
R01 GM051501 / GM / NIGMS NIH HHS / United States
R29 GM051501 / GM / NIGMS NIH HHS / United States
R01 GM072558-05 / GM / NIGMS NIH HHS / United States