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Published April 3, 1997 | public
Journal Article

Time-Dependent Stokes Shift and Its Calculation from Solvent Dielectric Dispersion Data

Abstract

The time-dependent solvation correlation function (the Stokes shift response function), which describes the solvent response to a sudden change in the charge distribution of a solute molecule, is calculated here directly from experimentally measured dielectric dispersion data, ε(ω), of the solvent. In the calculation a reaction field with the dielectric continuum assumption is used. This simple model is applied to the experimental results of Jimenez et al. for photoexcited coumarin and water as a solvent, and encouraging agreement is obtained using the experimental data on ε(ω).

Additional Information

© 1997 American Chemical Society. Received: October 8, 1996; In Final Form: January 13, 1997. It is a pleasure to acknowledge the support of this research by the National Science Foundation and by the Office of Naval Research. This article is dedicated to the memory of a long-time friend, Heinz Gerischer, whom one of us had the pleasure of knowing for almost 40 years. Heinz was a generous and thoughtful individual whose impact on electrochemistry is enormous.

Additional details

Created:
August 19, 2023
Modified:
October 23, 2023