The profiles of the potential of mean force for the <i>Cl^- - H₃O⁺</i> pair, as predicted by two <i>ab initio</i> models, are determined by constraint molecular dynamics simulation at a near-critical condition. The corresponding association constants are then determined and compared with that from conductance measurements to test the reliability of the current simulation models for <i>HCl</i>.

The theoretical treatment of the solvation phenomenon of simple ions in aqueous solutions has been rather difficult, despite the apparent simplicity of the system. Long-range solvent-screened electrostatic interactions, coupled to the large variation (with state conditions) of the dielectric permittivity of water, give rise to a variety of rather complex solvation phenomena including dielectric saturation, electrostriction, and ion association. Notably, ion solvation in high-temperature/pressure aqueous solutions plays a leading role in hydrothermal chemistry, such as in the natural formation of ore deposits, the corrosion in boilers and reactors, and in high-temperature microbiology. Tremendous effort has been invested in the study of hydrothermal solutions to determine their thermodynamic, transport, and spectroscopic properties with the goal of elucidating the solute-solvent and solute-solute interactions over a wide range of state conditions. It is precisely at these conditions where our understanding and predictive capabilities are most precarious, in part, as a result of the coexistence of processes with two rather different length scales, i.e., short-ranged (solvation) and long-ranged (compressibility-driven) phenomena (Chialvo and Cummings 1994a). The latter feature makes hydrothermal systems extremely challenging to model, unless we are able to isolate the (compressibility-driven) propagation of the density perturbation from the (solvation-related) finite-density perturbation phenomena (Chialvo …