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Density dependent vibrational relaxation in supercritical fluids

Myers, DJ and Shigeiwa, Motoyuki and Fayer, MD and Cherayil, Binny J (1999) Density dependent vibrational relaxation in supercritical fluids. In: Chemical Physics Letters, 313 (3-4). pp. 592-599.

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The vibrational lifetimes of the asymmetric CO stretching mode (1990 cm(-1)) of W(CO)(6) in the gas phase and as a function of density in supercritical ethane are examined using infrared pump-probe experiments. The gas phase measurement provides the zero density rate constant, which permits the effect of the ethane solvent to be separated from internal relaxation dynamics. The non-exponential gas phase vibrational dynamics are briefly discussed. The density dependence of the lifetime is compared to an extension of a hydrodynamic theory of vibrational relaxation in supercritical fluids to the regime of large wavevector. Agreement between experiment and theory is found to be good.

Item Type: Journal Article
Publication: Chemical Physics Letters
Publisher: Elsevier Science BV
Additional Information: Copyrights of this article belongs to Elsevier Science BV.
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited: 06 Mar 2009 07:02
Last Modified: 19 Sep 2010 05:01
URI: http://eprints.iisc.ac.in/id/eprint/18315

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