Contribution of Medium Phonons to the Transition Probability of Reactive Processes on Solid/Solution Interfaces. Joint Treatment of Classical and Quantum Parts of the Medium

Abstract

Quantumstatistical calculations are made of transition probabilities for reactive processes on solid/ liquid interfaces, which are assisted b y multi-phonon-transitions of the surrounding medium.A joint treatment of a classical (solvent) and a quanta1 (lattice) part of the medium effect upon reactive transitions is given. Numerical calculations are carried out in different approximations.Quantenstatistische Berechnung von ubergangswahrscheinlichkeiten fur reaktive Prozesse a n der Grenzflache fest/flussig werden durchgefiihrt. Diese sind von Multi-Phononen-Vbergiingen des umgebenden Mediums begleitet. Es wird eine gemeinsame Behandlung des klassischen (Solvens) und des Quanten-(Gitter) Medium-Effekts auf reaktive UbergBnge gegeben. Numerische Rechnungen werden auf verschiedenen Naherungsstnfen durchgefuhrt.

Chemical species conversion in condensed systems or at interfaces: quantum and classical regime of anharmonic Franck-Condon transitions

“…Lattice reorganization (process (III) addressed above), in addition to solvent reorganization, has been considered in [6,13], in the sudden approximation. Lattice equilibration after a perturbation should again be controlled classically.…”

Chemical Bond Formation Processes on Semiconductor Interfaces at Electronic Equilibrium or Nonequilibrium

“…An advantage of the transition matrix scheme following ( 5 ) is the capability of treating the coupling of the reactive process in the local reactive subsystem with multiphonon transitions in the medium [I, 22,231. Particular attention has been pnid recently to the development of absolute calculations of thermally averaged transition probabilities (P) in harmonic and anharmonic potentials [28], including the discussion of multidimensionality effects upon Franck-Condon overlap [29], and classical and quantum medium effects on reactive transitions [30]. The crucial factor in the numerical determination of species conversion probabilities ( P ) is the shape of the reactive local potential surfaces, which is a t the beginning of its CXploration.…”