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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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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
Publication: Bulletin of the Chemical Society of Japan
Publisher: The Chemical Society of Japan
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.ac.in/id/eprint/15404

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