Publication: A polarizable and flexible model for ethanol

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Title A polarizable and flexible model for ethanol
Authors/Editors* Shihao Wang, Natalie M. Cann
Where published* Journal of Chemical Physics
How published* Journal
Year* 2007
Volume 126
Number 214502
A polarizable, flexible model for ethanol is obtained based on an extensive series of B3LYP/6- 311++G(d,p) calculations and molecular dynamics simulations. The ethanol model includes electric field dependence in both the atomic charges and the intramolecular degrees of freedom. Field dependent intramolecular potentials have been attempted only once previously, for OH and HH stretches in water [P. Cicu, P. Demontis, S. Spanu, G. B. Suffritti, and A. Tilocca, J. Chem. Phys. 112, 8267 (2000)]. We find that the torsional potential involving the hydrogen-bonding hydrogen in ethanol is particularly field sensitive. Our methodology for developing field-dependent potentials can be readily generalized to other molecules and we discuss our procedures in detail. Molecular dynamics simulations of bulk ethanol are performed and the results are assessed based on comparisons with the self-diffusion coefficient [N. Karger, T. Vardag, and H. D. Ludemann, J. Chem. Phys. 93, 3437 (1990)], dielectric constant [J. T. Kindt and C. A. Schmuttenmaer, J. Phys. Chem. 100, 10373 (1996)], enthalpy of vaporization [R. C. Wilhoit and B. J. Zwolinski, J. Phys. Chem. Ref. Data, Suppl. 2 (1973)], and experimental interatomic distributions [C. J. Benmore and Y. L. Loh, J. Chem. Phys. 112, 5877 (2000)]. The simultaneous variation of the atomic charges and the intramolecular potentials requires modified equation of motion and we discuss the implementation of a multiple time step algorithm to solve these equations. The article concludes with a discussion of the bulk structure and properties with an emphasis on the hydrogen bonding network.
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