Deriving force fields with a multiscale approach: From ab initio calculations to molecular-based equations of state

EP Lyra and LFM Franco, JOURNAL OF CHEMICAL PHYSICS, 157, 114107 (2022).

DOI: 10.1063/5.0109350

Using theoretical and computational tools for predicting thermophysical properties of fluid systems and the soft matter has always been of interest to the physical, chemical, and engineering sciences. Certainly, the ultimate goal is to be able to compute these macroscopic properties from first-principles calculations beginning with the very atomic constitution of matter. In this work, Mie potential parameters were obtained through dimer interaction energy curves derived from ab initio calculations to represent methane and substituted-methane molecules in a spherical one-site coarse-grained model. Bottom-up-based Mie potential parameters of this work were compared with top-down-based ones from the statistical associating fluid theory (SAFT) models for the calculation of thermodynamic properties and critical point by molecular dynamics simulations and SAFT-VR Mie equation of state. Results demonstrated that bottom-up-based Mie potential parameters when averaging the Mie potential parameters of a representative population of conformers provide values close to the top-down-based ones from SAFT models and predict well properties of tetrahedral molecules. This shows the level of consistency embedded in the SAFT-VR Mie family of models and confers the status of a purely predictive equation of state for SAFT-VR Mie when a reasonable model is considered to represent a molecule of interest.

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