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Abstract Carbon dioxide (CO ₂ ) is prevalent in planetary atmospheres and sees use in a variety of industrial applications. Despite its ubiquitous nature, its photochemistry remains poorly understood. In this work we explore the density dependence of pressurized and supercritical CO ₂ electronic absorption spectra by vacuum ultraviolet spectroscopy over the wavelength range 1455-2000 Å. We show that the lowest absorption band transition energy is unaffected by a density increase up to and beyond the thermodynamic critical point (137 bar, 308 K). However, the diffuse vibrational structure inherent to the spectrum gradually decreases in magnitude. This effect cannot be explained solelymore » by collisional broadening and/or dimerization. We suggest that at high densities close proximity of neighboring CO ₂ molecules with a variety of orientations perturbs the multiple monomer electronic state potential energy surfaces, facilitating coupling between binding and dissociative states. We estimate a critical radius of ~4.1 Å necessary to cause such perturbations.« less

The lowest band in the charge-transfer-to-solvent ultraviolet absorption spectrum of aqueous chloride ion is studied by experiment and computation. Interestingly, the experiments indicate that at concentrations up to at least 0.25 M, where calculations indicate ion pairing to be significant, there is no notable effect of ionic strength on the spectrum. The experimental spectra are fitted to aid comparison with computations. Classical molecular dynamic simulations are carried out on dilute aqueous Cl^-, Na⁺, and NaCl, producing radial distribution functions in reasonable agreement with experiment and, for NaCl, clear evidence of ion pairing. Clusters are extracted from the simulations for quantummore » mechanical excited state calculations. Accurate ab initio coupled-cluster benchmark calculations on a small number of representative clusters are carried out and used to identify and validate an efficient protocol based on time-dependent density functional theory. The latter is used to carry out quantum mechanical calculations on thousands of clusters. The resulting computed spectrum is in excellent agreement with experiment for the peak position, with little influence from ion pairing, but is in qualitative disagreement on the width, being only about half as wide. It is concluded that simulation by classical molecular dynamics fails to provide an adequate variety of structures to explain the experimental CTTS spectrum of aqueous Cl^-.« less

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 andmore » 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.« less