Femtosecond solvation dynamics in acetonitrile: Observation of the inertial contribution to the solvent response

Journal of Chemical Physics - Tập 95 Số 6 - Trang 4715-4718 - 1991
Sandra J. Rosenthal1, X. Sunney Xie1, Meirong Du1, Graham R. Fleming1
1Department of Chemistry and the James Franck Institute, The University of Chicago, 5735 South Ellis Avenue, Chicago, Illinois 60637

Tóm tắt

The solvation dynamics of acetonitrile were characterized by a time resolved fluorescence shift measurement determined via the fluorescence upconversion technique. The solvation response is clearly two part in character. The fast initial relaxation accounts for ∼80% of the amplitude and is well fit by a Gaussian of 120 fs FWHM, giving a decay time of 70 fs. The slower tail is exponential with a decay time of ∼200 fs. Comparison of the results to molecular dynamics simulations performed by Maroncelli [J. Chem. Phys. 94, 2085 (1991)] reveal the fast initial part of the solvent response arises from small amplitude inertial rotational motion of molecules in the first solvation shell. The implications of a large amplitude, rapid inertial Gaussian component in the solvent response for theoretical descriptions of chemical reaction dynamics in solution are discussed.

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Journal of Chemical Physics

Tập 95 Số 6

4715-4718

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