Molecular integral equations theory in the near critical region of CO2

Environmental concerns are driving the search for greener yet efficient solvents. Supercritical CO 2 (scCO 2 ) is a promising candidate due to its non-toxicity and the potential for reusing CO 2 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 scCO 2 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 ultra-fast calculations. MDFT necessitates the bulk direct correlation functions, which can be calculated from expensive MD simulations or from approximate yet rapid molecular integral equation theories. The development of MDFT as a powerful tool to study the solvation in scCO 2 will require the construction of an accurate molecular integral equations for scCO 2 . In this perspective, this paper presents the exact direct correlation functions of scCO 2 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 CO 2 in scCO 2 . The results open the door to the application of MDFT to a wider range of solutes dissolved in scCO 2 , taking into account different thermodynamic conditions. • The combination of MD simulations and liquid-state theories permits to extract the correlations functions in the near-critical region of the supercritical CO 2 . • The molecular HNC theory reproduces well the MD-based correlation functions at all densities, except at long distances. • In the gas-like supercritical domain, the chemical potentials of CO 2 calculated with the classical DFT are in excellent agreement with the MD calculation.