A THEORY OF RADIATIONLESS TRANSITIONS
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Date
1962
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Publisher
Ohio State University
Abstract
A theory of radiationless transitions is developed according to the following model. Adiabatic, non-radiative transfer between two electronic states is assumed to be mediated via virtual radiative ''transitions'' to and from an intermediate electronic state. As in dispersion theory, the matrix element for the radiationless transition is then expressed in terms of the product of the matrix elements for the radiative components. By summing over all possible sublevels of the intermediate state, the total radiationless transition probability is obtained. The intermediate levels are virtual but serve to couple the initial and final states via the radiation field. Application of the theory in a very elementary form yields the correct relative magnitudes for the rates of internal conversion $(S_{2}\longrightarrow S_{1})$, intersystem crossing $(S_{1}\longrightarrow T_{1})$ and triplet-state deactivation $(T_{1} \longrightarrow S_{0})$. Further development of the theory centers around finding suitable approximations for the summation process.
Description
Author Institution: Quantum Chemistry Section, Space Technology Laboratories. Inc.