Ultraviolet charge-transfer-to-solvent spectroscopy of halide and hydroxide ions in subcritical and supercritical water.

The temperature dependence of the vacuum ultraviolet charge-transfer-to-solvent (CTTS) absorption spectra of aqueous halide and hydroxide ions was measured for the first time up to 380 °C in subcritical and supercritical water. With increasing temperature, absorption spectra are observed to broaden and redshift, much in agreement with previous measurements below 100 °C. These changes are discussed alongside classic cavity models of the solvated species, which tie in the configuration of the adjoining polarized medium and its critical role in light absorption for electronic transitions. The data seemingly confirm the validity of the "diffuse" model pioneered by Platzman and Franck and later revised by Stein and Treinin, which has largely gone untested for nearly 60 years due to lack of experimental data in this extended temperature range. A gradual increase in anion cavity size is inferred as a function of increasing temperature while the enthalpy and entropy of hydration are largely unaffected. The changes in solvation properties are considered in the context of recent studies of the ultraviolet spectroscopy of subcritical and supercritical water and historic studies of the CTTS absorption. The "diffuse" polarizable continuum model succeeds in describing the absorption due to lack of well-defined ion hydration shells for these ions. CTTS spectra for iodide in supercritical water show no energy shift as a function of pressure/density, suggesting dielectric saturation of the I- anion by the adjacent H2O molecules at all experimental pressures/densities.