Accurate Solvation Properties in Supercritical CO2 with Molecular Density Functional Theory.

Abstract

Supercritical CO2 is a highly efficient solvent for the development of more environmentally benign chemical processes. It is crucial to predict its solvation properties─the solvation free energy and the solvation structure─both accurately and at low computational cost. We show here that classical density functional theory (cDFT) can reproduce the solvation properties obtained from conventional molecular simulations, while requiring a computational effort that is several orders of magnitude lower. This excellent agreement is achieved using a molecular cDFT formalism based on a density that depends on both the positions and orientations of CO2 molecules in the vicinity of the solute. We further examine several levels of approximation for the excess free-energy functional in cDFT and demonstrate that the homogeneous reference fluid approximation is sufficient to recover the molecular dynamics (MD) benchmark results. These findings open the way to extending molecular cDFT to other thermodynamic conditions.