VIBRATIONAL LADDERS, STATE DENSITIES, AND DISSOCIATION PATHWAYS: APPLICATIONS OF SPECTROSCOPY TO LASER PHOTOCHEMISTRY

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1989

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Ohio State University

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Vibrational ladders of the spherical-top molecules $SiF_{1}, SF_{1}$, and $UF_{1}$ will be discussed. Special attention will be paid to the $\nu_{3}$ ladders, which can be easily pumped up to the vibrational ``quasicontinuum'' and on to dissociation. The differing vibrational state densities of these molecules result in differing behavior in multiphoton absorption and laser-induced photodissociation. Vibrational states have been calculated, with anharmonicity included, for these molecules for vibrational energies of up to $15,000 cm^{-1}$ and for state densities of up to $108 levels/cm^{-1}$; comparison will be made with the results of the approximation method of Whitten and $Rabinovitch.^{1}$ The effect of anharmonicity in increasing the state densities, and implications for photochemistry and thermodynamics, will be discussed.

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$^{1}$ G. Z. Whitten and B. S. Rabinovitch. J. Chem. Phys. 38. 2466 (1963).
Author Institution: University of California, Los Alamos National Laboratory

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