Theory of the time development of the stokes shift in polar media

Bagchi, Biman ; Oxtoby, David W. ; Fleming, Graham R. (1984) Theory of the time development of the stokes shift in polar media Chemical Physics, 86 (3). pp. 257-267. ISSN 0301-0104

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We present a theory for the time evolution of the Stokes shift of a polar molecule in a polar solvent. The time-dependent solute-solvent interaction is calculated in a continuum model by replacing the surrounding solvent by a frequency-dependent dielectric continuum. An expression for the time dependence of the fluorescence maximum is derived. This expression can be considered a direct generalization of the well-known Ooshika-Lippert-Mataga equation to the time domain. We also present an approximate expression for the wavelength dependence of the dynamics of the Stokes shift, and find it to be consistent with recent experimental results. We have investigated the effect of polarizability of the solute molecule and found that for many molecules this effect is not negligible.

Item Type:Article
Source:Copyright of this article belongs to Elsevier Science.
ID Code:4561
Deposited On:18 Oct 2010 07:32
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