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Relation between charge transfer absorption and fluorescence spectra and the inverted region

Marcus, R. A. (1989) Relation between charge transfer absorption and fluorescence spectra and the inverted region. Journal of Physical Chemistry, 93 (8). pp. 3078-3086. ISSN 0022-3654 . http://resolver.caltech.edu/CaltechAUTHORS:20150629-115003405

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Abstract

The theoretical expression for the plot of a charge transfer (CT) band intensity vs frequency is known to parallel that for the plot of electron-transfer rate constant k^(ET) vs –ΔG^0. We use this parallelism to explore a recent model in the literature on the possible role, if any, of partial dielectric saturation of the solvent on the “inverted region” of electron-transfer reactions. A simple approximate expression is obtained for the full width at half-maximum for the k^(ET) and spectral plots and is tested using recent numerical results for calculated k^(ET) vs –ΔG^0 curves. Studies of experimental widths of CT bands are used, thereby, to test ideas on the possible presence and effects of partial dielectric saturation and on the observation of the inverted region. Further uses of charge-transfer spectra, when both the absorption and fluorescence data are available, are also described, including the determination of the “0 → 0 transition energy” ΔE_( 0 → 0) for systems displaying little or no vibrational structure.


Item Type:Article
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http://dx.doi.org/10.1021/j100345a040DOIArticle
http://pubs.acs.org/doi/abs/10.1021/j100345a040PublisherArticle
Additional Information:© 1989 American Chemical Society. Received August 22, 1988; In Final Form October 7, 1988. It is a pleasure to acknowledge the support of this research by the Office of Naval Research, as well as very helpful discussions with N. Mataga, T. Kakitani, and S. Farid.
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Office of Naval Research (ONR)UNSPECIFIED
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Caltech Noyes Laboratory of Chemical Physics7825
Record Number:CaltechAUTHORS:20150629-115003405
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20150629-115003405
Official Citation:Marcus, R. A. (1989). Relation between charge transfer absorption and fluorescence spectra and the inverted region. The Journal of Physical Chemistry, 93(8), 3078-3086. doi: 10.1021/j100345a040
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:58670
Collection:CaltechAUTHORS
Deposited By: Joanne McCole
Deposited On:29 Jun 2015 20:06
Last Modified:29 Jun 2015 20:06

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