Ab initio development of generalized Lennard-Jones (Mie) force fields for predictions of thermodynamic properties in advanced molecular-based SAFT equations of state

A methodology for obtaining molecular parameters of a modified statistical associating fluid theory for variable-range interactions of Mie form (SAFT-VR Mie) equation of state (EoS) from ab initio calculations is proposed for non-associative species that can be modeled as single spherical segments. The methodology provides a strategy to map interatomic or intermolecular potentials obtained from ab initio quantum-chemistry calculations to the corresponding Mie potentials that can be used within the SAFT-VR Mie EoS. The inclusion of corrections for quantum and many-body effects allows for an excellent, fully predictive description of the vapor-liquid envelope and other bulk thermodynamic properties of noble gases; this description is of similar or superior quality to that obtained using SAFT-VR Mie with parameters regressed in the traditional way using experimental thermodynamic-property data. The methodology is extended to an anisotropic species, methane, where similar levels of accuracy are obtained. The efficacy of using less-accurate quantum-chemistry methods in this methodology is explored, showing that these methods do not provide satisfactory results, although we note that the description is nevertheless substantially better than those obtained using the conductor-like screening model for describing real solvents (COSMO-RS), the only other fully predictive ab initio method currently available. Overall, the reliance on thermophysical data is completely dispensed with, providing the first extensible, wholly predictive SAFT-type EoSs. (C) 2022 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license(http://creativecommons.org/licenses/by/4.0/).

Automated summary

This study proposes a methodology to obtain molecular parameters of SAFT-VR Mie equation of state from ab initio calculations, which can accurately describe the thermodynamic properties of non-associative species. The methodology includes corrections for quantum and many-body effects, and it outperforms the traditional regression method using experimental data. Additionally, the study reveals the limitations of using less-accurate quantum-chemistry methods.