Molecular integral equations theory in the near critical region of CO2

TL;DR

This paper evaluates molecular integral equations for supercritical CO2, comparing their accuracy in predicting solvation properties and demonstrating MDFT's potential for efficient solvation modeling in green chemistry applications.

Contribution

It provides the first comparison of MD-derived and HNC approximate direct correlation functions for scCO2, advancing MDFT as a practical tool for solvation predictions.

Findings

HNC captures short-range structure but not long-range correlations.

MD-derived functions improve accuracy of MDFT calculations.

Results enable MDFT application across various solutes and conditions.

Abstract

Environmental concerns are driving the search for greener yet efficient solvents. Supercritical CO2 (scCO2) is a promising candidate due to its non-toxicity and the potential for reusing CO2 emissions. It also offers a versatile range of properties that can be finely tuned by pressure adjustments. This adaptability is exploited in chemical industry processes such as separation or extraction. The development of new green processes using scCO2 requires an efficient tool for predicting the solvation properties under different conditions. Existing parametric equations for solubility prediction depend on known experimental data, while molecular dynamics (MD) simulations remain expensive for studying different conditions. Both methods are unsuitable for advancing new technologies. The molecular density functional theory (MDFT) offers a promising alternative, combining an accurate microscopic modeling with fast calculations. MDFT necessitates the bulk direct correlation functions, which can be calculated from expensive MD simulations or from approximate yet rapid molecular integral equations. The development of MDFT as a powerful tool to study the solvation in scCO2 will require the construction of an accurate molecular integral equations for scCO2.This paper presents the exact direct correlation functions of scCO2 obtained from MD and compares them with the results of the simplest molecular integral equations, the hypernetted chain approximation (HNC). If HNC fails to provide correct long-range correlations and thermodynamics, it succeeds in reproducing the short-range structure. By using the direct correlation functions obtained from MD and HNC, we demonstrate the efficacy of MDFT in calculating the chemical potential of CO2 in scCO2. The results open the door to the application of MDFT to a wider range of solutes dissolved in scCO2 with different thermodynamic conditions.