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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28 August 2011
Research Article|
August 26 2011
Time-dependent fluorescence in nanoconfined solvents: Linear-response approximations and Gaussian statistics
Brian B. Laird;
Brian B. Laird
a)
Department of Chemistry,
University of Kansas
, Lawrence, Kansas 66045, USA
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Ward H. Thompson
Ward H. Thompson
b)
Department of Chemistry,
University of Kansas
, Lawrence, Kansas 66045, USA
Search for other works by this author on:
Brian B. Laird
a)
Ward H. Thompson
b)
Department of Chemistry,
University of Kansas
, Lawrence, Kansas 66045, USA
a)
Electronic mail: [email protected].
b)
Electronic mail: [email protected].
J. Chem. Phys. 135, 084511 (2011)
Article history
Received:
March 08 2011
Accepted:
August 01 2011
Citation
Brian B. Laird, Ward H. Thompson; Time-dependent fluorescence in nanoconfined solvents: Linear-response approximations and Gaussian statistics. J. Chem. Phys. 28 August 2011; 135 (8): 084511. https://doi.org/10.1063/1.3626825
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