Solvent Stark Effect and Spectral Shifts

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Abstract
A theory is developed for the solvent shift in the electronic absorption spectrum of a nonpolar solute in a polar solvent. The shift is regarded as composed of two components, one of which arises from the same mechanism as the London forces and is taken successfully into account by the McRae theory. The second component, the solvent Stark effect, is treated in detail here by considering polarization fluctuations in a dipolar medium surrounding a cavity. A simple result for the contribution of this component in terms of the macroscopic dielectric properties of the solution is given. The model predicts in particular that the Stark contribution to the solvent shift becomes linear in the solution dielectric constant for large values of the latter. The theoretical expression obtained here is compared with the experimental data of Weigang and Wild for the 1La transition of naphthacene, and a satisfactory fit is obtained.

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