THE EFFECTS OF ADIABATIC AND NONADIABATIC INTERACTIONS ON VIBRONIC AND ELECTRIC FIELD SPECTRA
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Date
1974
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Ohio State University
Abstract
The results of recent theoretical work on nonadiabatic contributions to vibronic intensities are reported. Specifically, we consider the problem, in absorption, of how one takes into account the non-adiabaticity when its dependence on the total vibrational energy of the final vibronic state of the transition is not ignored. A simple perturbative scheme is developed which, although not applicable when the final vibronic state is in resonance with vibronic levels of the second interacting electronic state (higher energy), should prove useful for the off-resonance case. Model calculations are presented which show that for many systems the problem is soluble without knowledge of the geometry difference between the two interacting electronic states. Finally, the problem of adiabatic and nonadiabatic contributions to excited state dipole moments is considered along with some pertinent experimental data.
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Author Institution: Ames Laboratory-USAEC and Department of Chemistry, Iowa State University