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|
|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|
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