Georgievskii, Yuri and Hsu, Chao-Ping and Marcus, R. A. (1998) Dynamic Stokes shift in solution: Effect of finite pump pulse duration. Journal of Chemical Physics, 108 (17). pp. 7356-7366. ISSN 0021-9606 http://resolver.caltech.edu/CaltechAUTHORS:20090918-104720373
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The time-evolution of the fluorescence spectrum of a dissolved chromophore excited by an ultrafast pump pulse is considered. The average value of the energy difference of the solute in its excited and ground states is used to describe the relaxation of the maximum of the transient fluorescence spectrum to its equilibrium value (dynamic Stokes shift, DSS). A simple formula for the normalized DSS is obtained which generalizes an earlier standard classical expression and includes the effect of a pump pulse of finite duration. As an example, dielectric dispersion data are used for a dipolar solute in water to estimate the quantum correction to the standard DSS expression. The correction is negligible when the frequency of the pump pulse is close to the maximum in the absorption spectrum, but a deviation from the standard formula can be expected for the pump pulse tuned to a far wing of the absorption band of the chromophore. An expression is given for this deviation.
|Additional Information:||©1998 American Institute of Physics. Received 14 August 1997; accepted 27 January 1998. It is a pleasure to acknowledge the support of the National Science Foundation and the Office of Naval Research. One of us (Y.G.) would like to acknowledge the support of the James W. Glanville Postdoctoral Scholarship in Chemistry at Caltech and support in the early stages of this research of the Rueff-Wormser Fellowship. # 78.55.Bq Optical properties, condensed-matter spectroscopy and other interactions of radiation and particles with condensed matter Photoluminescence Liquids # 77.22.Ch Dielectrics, piezoelectrics, and ferroelectrics and their properties Dielectric properties of solids and liquids Permittivity (dielectric function)|
|Subject Keywords:||fluorescence, permittivity, ground states, excited states|
|Classification Code:||PACS: 78.55.Bq; 77.22.Ch|
|Official Citation:||Dynamic Stokes shift in solution: Effect of finite pump pulse duration Yuri Georgievskii, Chao-Ping Hsu, and R. A. Marcus, J. Chem. Phys. 108, 7356 (1998), DOI:10.1063/1.476155|
|Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||George Porter|
|Deposited On:||05 Oct 2009 18:08|
|Last Modified:||26 Dec 2012 11:24|
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