Chiroptical spectra of molecules with nearly degenerate electronic states

Abstract

The influence of vibronic interactions on the chiroptical spectra associated with pairs of nearly degenerate electronic transitions in chiral systems is examined on a formal theoretical model. We consider the special case in which two nearly degenerate electronic states are coupled by a single non-totally symmetric vibrational mode. Formal expressions are developed for the rotatory strengths of individual vibronic transitions in this coupled system. Calculations based on these expressions are carried out for a large number of parameter sets appropriate for various energy spacings between the unperturbed electronic states, vibronic coupling strengths, oscillator (vibrational mode) frequencies, and electronic rotatory strengths. The calculated results demonstrate the profound influence of vibronic interactions on the sign patterns and intensity distributions within the rotatory strength spectrum associated with the two coupled electronic states. The implications of these results for interpretations of circular dichroism spectra are discussed.

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Notes on contributors

F.S. Richardson

Fellow of the Camille and Henry Dreyfus Foundation.