TY - JOUR
T1 - Revisiting OPLS Force Field Parameters for Ionic Liquid Simulations
AU - Doherty, Brian
AU - Zhong, Xiang
AU - Gathiaka, Symon
AU - Li, Bin
AU - Acevedo, Orlando
N1 - Funding Information:
Gratitude is expressed to the National Science Foundation (CHE-1562205) and the Center for Computational Science at the University of Miami for support of this research.
Funding Information:
*(O.A.) E-mail: orlando.acevedo@miami.edu. ORCID Orlando Acevedo: 0000-0002-6110-3930 Funding Gratitude is expressed to the National Science Foundation (CHE-1562205) and the Center for Computational Science at the University of Miami for support of this research. Notes The authors declare no competing financial interest.
PY - 2017/12/12
Y1 - 2017/12/12
N2 - Our OPLS-2009IL force field parameters (J. Chem. Theory Comput. 2009, 5, 1038-1050) were originally developed and tested on 68 unique ionic liquids featuring the 1-alkyl-3-methylimidazolium [RMIM], N-alkylpyridinium [RPyr], and choline cations. Experimental validation was limited to densities and a few, largely conflicting, heat of vaporization (ΔHvap) values reported in the literature at the time. Owing to the use of Monte Carlo as our sampling technique, it was also not possible to investigate the reproduction of dynamics. The [RMIM] OPLS-2009IL parameters have been revisited in this work and adapted for use in molecular dynamics (MD) simulations. In addition, new OPLS-AA parameters have been developed for multiple anions, i.e., AlCl4-, BF4-, Br-, Cl-, NO3-, PF6-, acetate, benzoate bis(pentafluoroethylsulfonyl)amide, bis(trifluoroethylsulfonyl)amide, dicyanamide, formate, methylsulfate, perchlorate, propanoate, thiocyanate, tricyanomethanide, and trifluoromethanesulfonate. The computed solvent densities, heats of vaporization, viscosities, diffusion coefficients, heat capacities, surface tensions, and other relevant solvent data compared favorably with experiment. A charge scaling of ±0.8 e was also investigated as a means to mimic polarization and charge transfer effects. The 0.8-scaling led to significant improvements for ΔHvap, surface tension, and self-diffusivity; however, a concern when scaling charges is the potential degradation of local intermolecular interactions at short ranges. Radial distribution functions (RDFs) were used to examine cation-anion interactions when employing 0.8∗OPLS-2009IL and the scaled force field accurately reproduced RDFs from ab initio MD simulations.
AB - Our OPLS-2009IL force field parameters (J. Chem. Theory Comput. 2009, 5, 1038-1050) were originally developed and tested on 68 unique ionic liquids featuring the 1-alkyl-3-methylimidazolium [RMIM], N-alkylpyridinium [RPyr], and choline cations. Experimental validation was limited to densities and a few, largely conflicting, heat of vaporization (ΔHvap) values reported in the literature at the time. Owing to the use of Monte Carlo as our sampling technique, it was also not possible to investigate the reproduction of dynamics. The [RMIM] OPLS-2009IL parameters have been revisited in this work and adapted for use in molecular dynamics (MD) simulations. In addition, new OPLS-AA parameters have been developed for multiple anions, i.e., AlCl4-, BF4-, Br-, Cl-, NO3-, PF6-, acetate, benzoate bis(pentafluoroethylsulfonyl)amide, bis(trifluoroethylsulfonyl)amide, dicyanamide, formate, methylsulfate, perchlorate, propanoate, thiocyanate, tricyanomethanide, and trifluoromethanesulfonate. The computed solvent densities, heats of vaporization, viscosities, diffusion coefficients, heat capacities, surface tensions, and other relevant solvent data compared favorably with experiment. A charge scaling of ±0.8 e was also investigated as a means to mimic polarization and charge transfer effects. The 0.8-scaling led to significant improvements for ΔHvap, surface tension, and self-diffusivity; however, a concern when scaling charges is the potential degradation of local intermolecular interactions at short ranges. Radial distribution functions (RDFs) were used to examine cation-anion interactions when employing 0.8∗OPLS-2009IL and the scaled force field accurately reproduced RDFs from ab initio MD simulations.
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U2 - 10.1021/acs.jctc.7b00520
DO - 10.1021/acs.jctc.7b00520
M3 - Article
C2 - 29112809
AN - SCOPUS:85038223201
VL - 13
SP - 6131
EP - 6135
JO - Journal of Chemical Theory and Computation
JF - Journal of Chemical Theory and Computation
SN - 1549-9618
IS - 12
ER -