On contributions from non-Born–Oppenheimer corrections to the calculation of large distance electron transfer rates

Abstract

Vibronic coupling theory is formulated in an adiabatic Born–Oppenheimer approximation to investigate corrections to the calculation of large distance electron transfer rates arising from Born–Oppenheimer violation terms. Connections with the description of electron transfer in small ions and of radiative and nonradiative decay processes in molecules enable the qualitative assessment of the likely contributions from such terms. A discussion is provided of how certain anomolies in absorption intensities can be used to screen for possible candidates for non-Born–Oppenheimer contributions to large distance electron transfer rates. Peculiar aspects of a crude one-dimensional model treatment of the problem are also noted.