Transition Dipole-Solvent Interaction in Optical Electron Transfer.
Abstract
A new and fundamental feature of photoionization from solutions is presented. The oscillating transition dipole for electronic transitions from bound states in solution to the continuum interacts with the surrounding moleculars of the solvent. This interaction is similar to solvation. The transition dipole, oscillating at the frequency of the incident radiation, induces electronic polarization in the solvent. Thus, the minimum energy required for photoionization and the kinetic energy. This variation or shift resultsl from dielectric dispersion of the solvent and is displayed in dispersion spectra. Such dispersion shifts are fundamental to all photoionization process in condensed matter and thus a nonequilibriulm electronic contribution to the photoionization energy is required. Before this work, only the contribution from nuclear reorganization was recognized. This phenomenon may have significant effects on the photoionization rates and emission laws because of the rich structure of the dispersion spectra. The effect of ionic atmosphere screening on the dispersion shift is also investigated. Keywords: Dielectric dispersion; Photoemission.
Document Details
- Document Type
- Technical Report
- Publication Date
- Sep 30, 1986
- Accession Number
- ADA173340
Entities
People
- Andrew Dziedzic
- Paul Delahay
Organizations
- New York University