Calculation of the vibronic transition moment when the geometries of the combining states of the molecules are significantly different

The concept of the adiabatic approximation is introduced from a few new standpoints, and the conditions are refined under which we can assume that the total energy of an electronic-vibrational (vibronic) state is the sum of the energies of the “electronic” and the “nuclear” problems and the wave function is represented as the product of the corresponding functions. An expression exactly corresponding to such an approximation is considered for the optical transition matrix element, and its individual terms are analyzed for any change in the geometric structure of the molecule upon optical excitation. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 3, pp. 290–293, May–June, 2006.