Vibronic Interaction of Nearly Degenerate States in Substituted Benzene Anions

Abstract

The pseudo-Jahn—Teller effect, the vibronic interaction of nearly degenerate electronic states, arises in the same manner as the Jahn—Teller effect itself. An iteration method, suitable for desk calculation, has been developed to allow computation of the vibronic wavefunctions and energies of a system with two closely spaced electronic states. A calculation on benzene anion compares favorably with previously published results. The method, in combination with semiempirical evaluation of the necessary parameters, has been applied to various substituted benzene anions and the ESR spectra of these anions predicted. The results compare satisfactorily with experiment and indicate that the spectra are the net result of three principal factors, configuration interaction among the simple molecular orbital electronic states, vibronic coupling, and thermal equilibrium between at least two vibronic states.