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On the connection between Gaussian statistics and excited-state linear response for time-dependent fluorescence
Laird, Brian Bostian Thompson, Ward H.
Laird, Brian Bostian
Thompson, Ward H.
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Abstract
Time-dependent fluorescence (TDF) of a chromophore in a polar or nonpolar solvent is frequently simulated using linear-response approximations. It is shown that one such linear-response-type approximation for the TDF Stokes shift derived by Carter and Hynes [J. Chem. Phys.94, 5961 (1991)] that is based on excited-statedynamics gives the same result as that obtained by assuming Gaussian statistics for the energy gap. The derivation provides insight into the much discussed relationship between linear response and Gaussian statistics. In particular, subtle but important differences between the two approximations are illuminated that suggest that the result is likely more generally applicable than suggested by the usual linearization procedure. In addition, the assumption of Gaussian statistics directly points to straightforward checks of the validity of the approximation with essentially no additional computational effort.
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This is the publisher's version, also available electronically from http://scitation.aip.org/content/aip/journal/jcp/126/21/10.1063/1.2747237.
Date
2007-06-06
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American Institute of Physics
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Laird, Brian Bostian; Thompson, Ward H. (2007). "On the connection between Gaussian statistics and excited-state linear response for time-dependent fluorescence." The Journal of Chemical Physics, 126(21):211104. http://dx.doi.org/10.1063/1.2747237.