Time-dependent fluorescence in nanoconfined solvents: Linear-response approximations and Gaussian statistics

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Issue Date
2011-08-26Author
Laird, Brian Bostian
Thompson, Ward H.
Publisher
American Institute of Physics
Type
Article
Article Version
Scholarly/refereed, publisher version
Metadata
Show full item recordAbstract
The time-dependent fluorescence of a model dye molecule in a nanoconfined solvent is used to test approximations based on the dynamic and static linear-response theories and the assumption of Gaussian statistics. Specifically, the results of nonequilibrium molecular-dynamics simulations are compared to approximate expressions involving time correlation functions obtained from equilibrium simulations. Solvation dynamics of a model diatomic dye molecule dissolved in acetonitrile confined in a spherical hydrophobic cavity of radius 12, 15, and 20 Å is used as the test case. Both the time-dependent fluorescence energy, expressed as the normalized dynamic Stokes shift, and the time-dependent position of the dye molecule after excitation are examined. While the dynamic linear-response approximation fails to describe key aspects of the solvation dynamics, assuming Gaussian statistics reproduces the full nonequilibrium simulations well. The implications of these results are discussed.
Description
This is the publisher's version, also available electronically from http://scitation.aip.org/content/aip/journal/jcp/135/8/10.1063/1.3626825.
ISSN
0021-9606Collections
Citation
Laird, Brian Bostian; Thompson, Ward H. (2011). "Time-dependent fluorescence in nanoconfined solvents: Linear-response approximations and Gaussian statistics. The Journal of Chemical Physics, 135(8):084511. http://dx.doi.org/10.1063/1.3626825
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