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Cage Dynamics in the Third-Order Off-Resonant Response of Liquid Molecules: A Theoretical Realization

Okumura, Ko and Bagchi, Biman and Tanimura, Yoshitaka (2000) Cage Dynamics in the Third-Order Off-Resonant Response of Liquid Molecules: A Theoretical Realization. In: Bulletin of the Chemical Society of Japan, 73 (4). pp. 873-884.

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Abstract

It is generally believed that the ultrafast initial spectroscopic response from the molecules in the condensed phase originates from small amplitude inertial motions within the cage formed by the nearest-neighbor solvent molecules surrounding the probe, or the cage effect. However, no quantitative estimate of this dynamics has been available for the currently popular experiments which measure the third-order off-resonant response. In this work, we fill this gap by a microscopic approach and demonstrate that the cage dynamics alone can produce the initial rise in the subpicosecond (ca. 200 fs) range in the third-order response. A simple analytical expression for the initial Gaussian time constant relevant to various kinds of the third-order off-resonant experiments is presented, which is found to be rather strongly dependent on the temperature. Connection with the non-polar solvation dynamics is also discussed.

Item Type: Journal Article
Additional Information: Copyright of this article belongs to The Chemical Society of Japan.
Department/Centre: Division of Chemical Sciences > Solid State & Structural Chemistry Unit
Date Deposited: 04 Aug 2008
Last Modified: 27 Aug 2008 13:40
URI: http://eprints.iisc.ernet.in/id/eprint/15404

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