Thermophysical properties prediction: towards a unified approach
Résumé
Developing a generic force field, that, when combined with molecular simulations, allows to
predict both transport and equilibrium properties of fluids in various thermodynamics conditions
is still a challenge [1-3]. Fine Grained (FG) force fields are the most popular ones, but their
parameterizations are not an easy task and are often done on equilibrium properties only. As
an alternative Coarse Grained (CG) force fields possess several interesting features relatively
to FG models. First, they are simpler to parameterize. Second, they require a smaller amount
of CPU time. Third, if appropriately chosen, they can be combined with theories to directly
predict their properties avoiding then the need of molecular simulations.
Among the available CG force fields, the one based on the Lennard-Jones (LJ) chain, that
consists in LJ particles freely and tangentially bonded, is known to describe well the equilibrium
properties with only three parameters per non polar species, as exemplified by the success of
some SAFT equations of state. However, this molecular model is not able to yield accurate
transport properties, such as viscosity, of molecular fluids [1]. To alleviate this weakness a
forth molecular parameter can be added as done when the LJ potential is replaced by Mie
potential [2, 4]. This Mie CG force field provides very good results for small molecular
compounds [4], but exhibit a systematic underestimation of the liquid viscosity [5], explained
by the fully flexible nature of the molecules represented by such CG force field.
Thus, in this work, we propose a new CG force field that integrates a variable rigidity in a
LJ chain model as the additional forth parameter, named hereafter the RLJC force field. To
determine the four molecular parameters, we have employed a top-down parameterization
strategy thanks to the principle of corresponding states, similarly to what proposed in refs [2]
and [4]. It will be shown during the presentation that this simple CG force field is able to provide
good thermodynamic and transport properties of various compounds for a wide range of
thermodynamics conditions.
References:
[1] G. Galliéro, 2014. Equilibrium, Interfacial and Transport properties of n-alkanes:
towards the simplest coarse grained molecular model. Chem. Eng. Res. Des. 92, 3031−3037.
[2] H. Hoang, S. Delage-Santacreu, G. Galliero, 2017. Simultaneous description of equilibrium,
interfacial and transport properties of fluids using a Mie Chain Coarse-Grained Force Field.
Ind. Eng. Chem. Res. 56, 32, 9213–9226.
[3] S. Rahman , O. Lobanova , G. Jiménez-Serratos , C. Braga , V. Raptis , E. A. Müller , G.
Jackson , C. Avendaño , A. Galindo. 2018. SAFT‑γ Force Field for the Simulation of Molecular
Fluids. 5. Hetero-Group Coarse-Grained Models of Linear Alkanes and the Importance of
Intramolecular Interactions. J. Phys. Chem. B 122, 9161−9177.
[4] A. Mejía, C. Herdes, E. A. Müller, 2014. Force Fields for Coarse-Grained Molecular
Simulations from a Corresponding States Correlation Industrial & Engineering Chemistry.
Research 53 (10), 4131-4141.
[5] A. W. Saley Hamani, J. P. Bazile, H. Hoang, H. T. Luc, J. L. Daridon, G. Galliero, 2020.
Thermophysical properties of simple molecular liquid mixtures: On the limitations of some force
fields. Journal of Molecular Liquids, 303, 112663.