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Time-dependent fluorescence in nanoconfined solvents: Linear-response approximations and Gaussian statistics
Laird, Brian Bostian Thompson, Ward H.
Laird, Brian Bostian
Thompson, Ward H.
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Abstract
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.
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This is the publisher's version, also available electronically from http://scitation.aip.org/content/aip/journal/jcp/135/8/10.1063/1.3626825.
Date
2011-08-26
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American Institute of Physics
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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