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Vibrational Lifetimes and Spectral Shifts in Supercritical Fluids as a Function of Density: Experiments and Theory

Myers, DJ and Shigeiwa, Motoyuki and Fayer, MD and Cherayil, Binny J (2000) Vibrational Lifetimes and Spectral Shifts in Supercritical Fluids as a Function of Density: Experiments and Theory. In: Journal of Physical Chemistry A, 104 (10). pp. 2402-2414.

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Vibrational lifetime and spectral shift data for the asymmetric CO stretching mode of $W(CO)_6$ in supercritical ethane, carbon dioxide, and fluoroform as a function of density at two temperatures are presented, and the lifetime $(T_1)$ measurements are compared to theory. The data and theory are refinements of previous work. Measurements at zero density allow the contribution from solute-solvent interactions to be separated from strictly intramolecular contributions to $T_1$. The results in the polyatomic SCFs are compared to data in Ar. The density functional/thermodynamic $theory^1$ has been extended to include contributions at large wavevector (k). Very good, quantitative agreement between theory and data taken in ethane and fluoroform is achieved, but the agreement for data taken in carbon dioxide, while reasonable, is not as good. The theory uses a variety of input information on the SCF properties obtained from the fluids' equations of state and other tabulated thermodynamic data. The solute-solvent spatial distribution is described in terms of hard spheres. The theory is able to reproduce the data without solute-solvent attractive interactions or clustering in the calculation of the spatial distribution.

Item Type: Journal Article
Publication: Journal of Physical Chemistry A
Publisher: American Chemical Society
Additional Information: Copyright of this article belongs to American Chemical Society.
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited: 19 Sep 2008 06:09
Last Modified: 19 Sep 2010 04:49
URI: http://eprints.iisc.ac.in/id/eprint/15858

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