Electronic Resource
College Park, Md.
:
American Institute of Physics (AIP)
The Journal of Chemical Physics
84 (1986), S. 936-944
ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
The energetics of photoionization in condensed phases includes a significant contribution from nonequilibrium processes arising from dielectric dispersion of the solvent at the prevailing photon energy. The solvent is polarized by the varying electric field caused by the change of ionic valence as a result of photoionization. This ionic field varies in a time interval determined by the frequency of incident radiation. The following contributions from nonequilibrium processes to the energetics of photoionization are calculated for transparent and absorbing solvents: electronic polarization, London dispersion, and Born repulsion energies for a discrete model of coordinated solvent molecules in the inner-sphere solvation shell of anions and cations; electronic polarization of the outer-sphere region for a continuous medium model. The losses resulting from the rapid variation of the ionic field for an absorbing solvent are calculated for the inner- and outer-sphere regions, respectively, from a discrete model and a continuous medium. Damping of the ionic field resulting from solvent absorption is negligible. The theory is applied to aqueous solutions in the 7–10.4 eV range of photon energies by using dielectric data from reflectance spectroscopy of liquid water. Experimental dispersion spectra for photoelectron emission have the shape predicted by theory and display all the extrema at the photon energies of the calculated curves. The very pronounced effect of ionic strength on the balance between inner- and outer-sphere contributions predicted by theory (inner–outer sphere splitting) is fully confirmed by experiment. Dispersion spectra of inorganic ions in the range of each of the two absorption bands of liquid water (maxima at ∼8.2 and 10.0 eV) therefore exhibit a double maximum for normal dispersion and a double minimum for anomalous dispersion (12 extrema between 7.2 and 10.4 eV). Specific effect of the nature of anions is evident above 9.0 eV in inner–outer spheresplitting. The present study provides a way of probing the response of liquids and solutions to the rapidly varying intense ionic field resulting from the process of photoionization.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.450539
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