The effect of solvent environment on molecular electronic oscillator strengths

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Abstract
A simple expression is derived for the effect of solvent environment on solute oscillator strength. The only parameters required are the refractive index of the solvent and a geometric factor which depends upon the shape of the molecule and the orientation of its transition moment. Whereas classical local field theories predict that oscillator strengths in all molecules should change in the same direction with increasing solvent polarizability, our theory correctly predicts a decrease in the oscillator strength of the π*←π transition of β‐carotene and an increase in the oscillator strength of the π*←n transition in pyrazine. The theory is based on perturbation of the ground and excited states of the solute by point–dipole interactions between solvent and solute transition moments. Although our expression is derived for nonpolar solutes in nonpolar solvents, experimental evidence indicates that it may be equally applicable to nonpolar solutes in polar solvents.

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