Polarizable empirical force field for the primary and secondary alcohol series based on the classical drude model

Victor M. Anisimov, Igor Vorobyov, Benoît Roux, Alexander D. MacKerell

Research output: Contribution to journalArticle

117 Citations (Scopus)

Abstract

A polarizable empirical force field based on the classical Drude oscillator has been developed for the aliphatic alcohol series. The model is optimized with an emphasis on condensed-phase properties and is validated against a variety of experimental data. Transferability of the developed parameters is emphasized by the use of a single electrostatic model for the hydroxyl group throughout the alcohol series. Aliphatic moiety parameters were transferred from the polarizable alkane parameter set, with only the Lennard-Jones parameters on the carbon in methanol optimized. The developed model yields good agreement with pure solvent properties with the exception of the heats of vaporization of 1-propanol and 1-butanol, which are underestimated by approximately 6%; special LJ parameters for the oxygen in these two molecules that correct for this limitation are presented. Accurate treatment of the free energies of aqueous solvation required the use of atom-type specific Oalcohol-O water LJ interaction terms, with specific terms used for the primary and secondary alcohols. With respect to gas-phase properties the polarizable model overestimates experimental dipole moments and quantum mechanical interaction energies with water by approximately 10 and 8%, respectively, a significant improvement over 44 and 46% overestimations of the corresponding properties in the CHARMM22 fixed-charge additive model. Comparison of structural properties of the polarizable and additive models for the pure solvents and in aqueous solution shows significant differences indicating atomic details of intermolecular interactions to be sensitive to the applied force field. The polarizable model predicts pure solvent and aqueous phase dipole moment distributions for ethanol centered at 2.4 and 2.7 D, respectively, a significant increase over the gas-phase value of 1.8 D, whereas in a solvent of lower polarity, benzene, a value of 1.9 is obtained. The ability of the polarizable model to yield changes in the dipole moment as well as the reproduction of a range of condensed-phase properties indicates its utility in the study of the properties of alcohols in a variety of condensed-phase environments as well as representing an important step in the development of a comprehensive force field for biological molecules.

Original languageEnglish (US)
Pages (from-to)1927-1946
Number of pages20
JournalJournal of Chemical Theory and Computation
Volume3
Issue number6
DOIs
StatePublished - Nov 1 2007
Externally publishedYes

Fingerprint

field theory (physics)
alcohols
Alcohols
Dipole moment
dipole moments
Gases
vapor phases
moment distribution
heat of vaporization
1-Propanol
1-Butanol
Molecules
Alkanes
Water
Solvation
interactions
Propanol
Benzene
Butenes
Vaporization

ASJC Scopus subject areas

  • Computer Science Applications
  • Physical and Theoretical Chemistry

Cite this

Polarizable empirical force field for the primary and secondary alcohol series based on the classical drude model. / Anisimov, Victor M.; Vorobyov, Igor; Roux, Benoît; MacKerell, Alexander D.

In: Journal of Chemical Theory and Computation, Vol. 3, No. 6, 01.11.2007, p. 1927-1946.

Research output: Contribution to journalArticle

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abstract = "A polarizable empirical force field based on the classical Drude oscillator has been developed for the aliphatic alcohol series. The model is optimized with an emphasis on condensed-phase properties and is validated against a variety of experimental data. Transferability of the developed parameters is emphasized by the use of a single electrostatic model for the hydroxyl group throughout the alcohol series. Aliphatic moiety parameters were transferred from the polarizable alkane parameter set, with only the Lennard-Jones parameters on the carbon in methanol optimized. The developed model yields good agreement with pure solvent properties with the exception of the heats of vaporization of 1-propanol and 1-butanol, which are underestimated by approximately 6{\%}; special LJ parameters for the oxygen in these two molecules that correct for this limitation are presented. Accurate treatment of the free energies of aqueous solvation required the use of atom-type specific Oalcohol-O water LJ interaction terms, with specific terms used for the primary and secondary alcohols. With respect to gas-phase properties the polarizable model overestimates experimental dipole moments and quantum mechanical interaction energies with water by approximately 10 and 8{\%}, respectively, a significant improvement over 44 and 46{\%} overestimations of the corresponding properties in the CHARMM22 fixed-charge additive model. Comparison of structural properties of the polarizable and additive models for the pure solvents and in aqueous solution shows significant differences indicating atomic details of intermolecular interactions to be sensitive to the applied force field. The polarizable model predicts pure solvent and aqueous phase dipole moment distributions for ethanol centered at 2.4 and 2.7 D, respectively, a significant increase over the gas-phase value of 1.8 D, whereas in a solvent of lower polarity, benzene, a value of 1.9 is obtained. The ability of the polarizable model to yield changes in the dipole moment as well as the reproduction of a range of condensed-phase properties indicates its utility in the study of the properties of alcohols in a variety of condensed-phase environments as well as representing an important step in the development of a comprehensive force field for biological molecules.",
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