Exact solution of three-level model of excited state electron transfer symmetry breaking in quadrupolar molecules.

Abstract

An analytical solution of a three-level model of symmetry breaking in excited AL-D-AR quadrupolar triads with an electron donor D and identical electron acceptors AL and AR is derived, in particular, an analytical expression for the dissymmetry parameter (difference in charges, in electron charge units, on the left and right arms of the molecule) is obtained. The model predicts the threshold dependence of the symmetry breaking degree on the parameters of the molecule and its interaction with the solvent. It is shown that for typical molecular parameters, symmetry breaking occurs as a charge transfer from one arm of the molecule to the other with nearly invariable donor charge. A considerable variation of the donor charge in the course of symmetry breaking is predicted for triads with small energy gap between the ground and first excited states. Analysis of the results shows that for a large parameter area, they are very similar to those obtained in a much simpler two-level model, which suggests that instead of a more realistic three-level model, we can use a two-level model to describe symmetry breaking in excited quadrupole molecules. The theory of symmetry breaking effect on the intramolecular vibrational spectra is developed. A comparison of the effect of solvent polarity on IR spectra changes due to an increase in the degree of symmetry breaking with the available experimental data shows that the model adequately describes this phenomenon.