Influence of the Lennard-Jones Combination Rules on the Simulated Properties of Organic Liquids at Optimal Force-Field Parametrization

• DOI: 10.1021/acs.jctc.2c01170
• Publication Date: 2023-03-15T16:42:38Z
• Authors: Marina P. Oliveira; Philippe H. Hünen...
• Keywords: Parametrization (atmospheric modeling); Force Field; Combining rules; Vaporization

We recently introduced the CombiFF scheme [Oliveira et al., J. Chem. Theory Comput. 2020, 16, 7525], an approach for automated refinement of force-field parameters against experimental condensed-phase data large compound families. Using this scheme, once time-consuming task target-data selection and curation has been performed, optimization itself is both straightforward fast. As a result, provides ideal framework evaluating influence functional-form decisions on accuracy force field at optimal level parametrization. already used to assess effect using all-atom representation compared united-atom representations in 2022, 18, 6757]. Here, applied three Lennard-Jones combination rules, geometric-mean (GM), Lorentz-Berthelot (LB), or Waldman-Hagler (WH), simulated properties organic liquids. The comparison performed terms liquid density ρliq, vaporization enthalpy ΔHvap, surface-tension coefficient γ, static relative dielectric permittivity ϵ, self-diffusion D. calibrations variants are carried out independently 2044 values ΔHvap concerning 1516 compounds. resulting root-mean-square deviations from experiment 30.0, 26.9, 36.7 kg m-3 ρliq 2.8, 2.9 kJ mol-1 when applying GM, LB, WH respectively. In these (and other) properties, rules perform comparatively well, with GM LB results being more similar each other slightly accurate experiment. contrast, use distinct parameter calibration property calculation leads much larger errors.