Time-dependent fluorescence spectra of large molecules in polar solvents
Abstract
A method is described for incorporating the vibronic transitions of a solute molecule in the calculation of the time evolution of its fluorescence spectrum in a polar solvent. In this initial article, systems are treated in which the intramolecular vibrational relaxation is much faster than the observed delay time. The overall fluorescence spectrum is then shown to be a convolution of the steady-state absorption and emission spectra of the solute in a nonpolar solvent and the time-dependent emission line shape arising only from polar interactions. Calculations are made for coumarin 153 in acetonitrile, using the dielectric dispersion data of the solvent available from experimental measurements. The results are in encouraging agreement with experimental spectra. Results are also given for the dynamic Stokes shift in methanol.
Additional Information
© 1998 American Chemical Society. Received: November 19, 1997. We wish to particularly thank Professor J. E. Bertie for providing the data file and the computer code on the dielectric dispersion of acetonitrile before publication. It is a pleasure to acknowledge the support of the National Science Foundation and the Office of Naval Research. Y.G. would like to acknowledge the support of the James W. Glanville Postdoctoral Scholarship in Chemistry at Caltech and the support in the early stages of this research by a Rueff-Wormser Fellowship.Additional details
- Eprint ID
- 58101
- Resolver ID
- CaltechAUTHORS:20150609-082842994
- NSF
- Office of Naval Research (ONR)
- James W. Glanville Postdoctoral Scholarship
- Rueff-Wormser Fellowship
- Created
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2015-06-09Created from EPrint's datestamp field
- Updated
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2021-11-10Created from EPrint's last_modified field