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Polarizable Empirical Force Field for Acyclic Polyalcohols Based on the Classical Drude Oscillator
Author(s) -
He Xibing,
Lopes Pedro E. M.,
MacKerell Alexander D.
Publication year - 2013
Publication title -
biopolymers
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.556
H-Index - 125
eISSN - 1097-0282
pISSN - 0006-3525
DOI - 10.1002/bip.22286
Subject(s) - polarizability , chemistry , force field (fiction) , intermolecular force , dipole , hydrogen bond , computational chemistry , molecule , thermodynamics , chemical physics , vicinal , transferability , organic chemistry , quantum mechanics , physics , mathematics , statistics , logit
A polarizable empirical force field for acyclic polyalcohols based on the classical Drude oscillator is presented. The model is optimized with an emphasis on the transferability of the developed parameters among molecules of different sizes in this series and on the condensed‐phase properties validated against experimental data. The importance of the explicit treatment of electronic polarizability in empirical force fields is demonstrated in the cases of this series of molecules with vicinal hydroxyl groups that can form cooperative intra‐ and intermolecular hydrogen bonds. Compared to the CHARMM additive force field, improved treatment of the electrostatic interactions avoids overestimation of the gas‐phase dipole moments resulting in significant improvement in the treatment of the conformational energies and leads to the correct balance of intra‐ and intermolecular hydrogen bonding of glycerol as evidenced by calculated heat of vaporization being in excellent agreement with experiment. Computed condensed phase data, including crystal lattice parameters and volumes and densities of aqueous solutions are in better agreement with experimental data as compared to the corresponding additive model. Such improvements are anticipated to significantly improve the treatment of polymers in general, including biological macromolecules. © 2013 Wiley Periodicals, Inc. Biopolymers 99: 724–738, 2013.