Structure of aqueous solutions of tons and neutral solutes at infinite dilution at a supercritical temperature of 683 K

We discuss the structure of alkali metal ions, halide ions, and uncharged s olutes at infinite dilution in supercritical water solutions, at solvent de nsities of 0.35, 0.20, and 0.997 g cm(-3) at a temperature of 683 K using t he SPC/E model for water. This model has critical constants (T-e = 640 K, r ho (c) = 0.29 g cm(-3)) which compare well with the corresponding values (T -e = 647 K, rho (c) = 0.322 g cm(-3)) for real water. The solute-water pair correlation functions are qualitatively different for the charged and unch arged solutes at 683 K at both 0.35 and 0.20 g cm(-3) solvent densities, wi th water expelled from the immediate vicinity of the uncharged solute but r etained and compressed in the neighborhood of a small ion. Increasing the s olvent density to 0.997 g cm(-3) at 683 K leads to dramatic changes in the solvent structure around an uncharged solute, with the formation of hydroge n-bonded cages analogous to those observed at room temperature (298 K) at t he same solvent density. The primary hydration numbers of the ions at 683 K and solvent density of 0.35 g cm(-3) are nearly the same as the correspond ing values at room temperature at a solvent density of 0.997 g cm(-3). The partial molar volumes of the ions and uncharged species at the supercritica l temperature are different in sign and are explained in terms of a simple model. The dynamics of ions and uncharged solutes under the same supercriti cal conditions are discussed in the companion to this paper.