Quantum theory of chemical bond formation processes in condensed systems: studies towards exploration of electrochemical dark and photoprocesses on semiconductors

Abstract

Quantum theoretical models of chemical bond formation and partial charge transfer processes in condensed systems, and their extension to processes in electronic non-equilibrium are investigated in this paper with a view to further exploration of electrochemical and photoelectrochemical kinetics on semiconductors. Electrochemical dark and photocurrents on n-III-V-semiconductors are correlated with calculated transition probabilities for atom-group transfer over larger distances (80 to 240 pm), leading to a first estimate of potential surface shapes compatible with experiment. Some specific problems connected with transition probability calculations for heavy-particle transfer in strong anharmonic potentials are considered in detail, including approximation of Franck-Condon transitions in arbitrary potentials by their classical limit.