Nonequilibrium Electronic Polarization of the Solvent in Photoionization.
Abstract
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 the 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 photoinization are calculated for transparent and absorbing solvents: electronic photoionization, 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. The theory is applied to aqueous solutions in the 7 to 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.
Document Details
- Document Type
- Technical Report
- Publication Date
- Jul 01, 1985
- Accession Number
- ADA157479
Entities
People
- A. Dziedzic
- Paul Delahay
Organizations
- New York University