Title
Force Field Parametrization from the Hirshfeld Molecular Electronic Density
Date Issued
13 November 2018
Access level
metadata only access
Resource Type
journal article
Author(s)
Pérez De La Luz A.
Méndez-Bermúdez J.G.
Alejandre J.
Universidad Autónoma Metropolitana
Publisher(s)
American Chemical Society
Abstract
The Hirshfeld charges are linearly increased to reproduce the experimental dielectric constant of 10 polar solvents having values between 13 (pyridine) and 182 (N-methylformamide). The OPLS/AA force field is used to obtain the new parameters. The surface tension and liquid density are also target properties to determine the new nonbonding parameters. The charge scaling factor is between 1.2 and 1.3. In addition, properties that were not used in the parametrization procedure, such as the heat of vaporization, self-diffusion coefficient, shear viscosity, isothermal compressibility, and volumetric expansion coefficient are obtained. Binary mixtures of amide/water and amide/amide are also studied. The original parameters of OPLS/AA, CGenFF, and GAFF force fields are evaluated. The TIP4P/ϵ force field is used to simulate water. The results from this work with the new parameters, for both pure components and binary mixtures, are in better agreement with experimental data than those obtained with the original values for most of the calculated properties. The maximum density of N-methylformamide in aqueous solutions is correctly predicted only with the new parameters. The high value of the dielectric constant of acetamide, formamide, and N-methylformamide is discussed in terms of the chain formation from the hydrogen bond interactions.
Start page
5949
End page
5958
Volume
14
Issue
11
Language
English
OCDE Knowledge area
Nano-materiales Ingeniería de procesos
Scopus EID
2-s2.0-85055623479
PubMed ID
Source
Journal of Chemical Theory and Computation
ISSN of the container
15499618
Sponsor(s)
We thank to Laboratorio de Supercomputó y Visualizacioń en Paralelo for the time provided to develop this work, to Professor José Luis Gaźquez for helpful discussions about the Hirshfeld method and to Conacyt for financial support under the project 257422. APL thanks Conacyt for a PhD scholarship. Consejo Nacional de Ciencia y Tecnología 257422 CONACYT
Sources of information: Directorio de Producción Científica Scopus