ENVIRONMENTAL EFFECTS ON RADIATIVE RATE CONSTANTS FOR LINEAR POLYENES

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Title: ENVIRONMENTAL EFFECTS ON RADIATIVE RATE CONSTANTS FOR LINEAR POLYENES
Creators: Andrews, John R.; Hudson, Bruce S.
Issue Date: 1977
Publisher: Ohio State University
Abstract: The radiative rate constants of diphenylhexatriene and transretinol are calculated from published values of the fluorescence lifetime and quantum $yield.^{1,2}$ The variations in the calculated rate constants with solvent and temperature are quantitatively explained by a theoretical expression, relating the radiative rate constant of a forbidden transition to the amount of mixing with a single allowed $transition.^{3}$ The mixing is inversely proportional to the energy separation of the two states. Increasing the solvent polarizability decreases the energy gap leading to increased mixing. Extension of a relation between radiative lifetime and absorption $intensity^{4}$ permits an estimate of the energy gap between the states and the magnitude of the mixing matrix element.
Description: $^{1}$E. D. Cehelnik, R. B. Cundall, J. R. Lockwood, and T. F. Palmer, J. Phys. Chem. 79, 1369 (1975). $^{2}$J. P. Dalle and B. Rosenberg, Photochem. and Photobiol. 12, 151 (1970). $^{3}$B. S. Hudson and B. E. Kohler, J. Chem. Phys. 59, 4984 (1973). $^{4}$S. J. Strickler and R. A. Berg, J. Chem. Phys. 37, 814 (1962).
Author Institution: Department of Chemistry, Stanford University
URI: http://hdl.handle.net/1811/10046
Other Identifiers: 1977-MG-8
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