Abstract
ABSTRACT Download : Download full-size image Molecular anions that possess excess internal vibrational and/or rotational energy can eject their “extra” electron through a radiationless transition event involving non Born-Oppenheimer coupling. In such processes, there is an interplay between the nuclear and electronic motions that allows energy to be transferred from the former to the latter and that permits momentum and/or angular momentum to also be transferred in a manner that preserves total energy, momentum, and angular momentum. There are well established quantum mechanical expressions for the rates of this kind of radiationless process, and these expressions have been used successfully to compute electron ejection rates. In this paper, we recast the quantum rate equation into more physically clear forms by making use of semi-classical approximations that have proven useful in rewriting the quantum expressions for rates of other processes (e.g., photon absorption) in a more classical manner. It is hoped that by achieving alternative and clearer interpretations of the electron ejection rate equation, it will be possible to more readily predict when such rates will be significant.
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