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Vibrational Relaxation Rates and Pathways in Highly Excited Molecules.
Final rept. 30 Jun 82-29 Jun 85,
WISCONSIN UNIV-MADISON DEPT OF CHEMISTRY
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The techniques of laser double resonance or near-infrared fluorescence detection in combination with direct excitation of overtone vibrations provide detailed data on the rates and pathways of collisional energy transfer in hydrogen fluoride and deuterium fluoride. These measurements yield the self-relaxation rate constants for HFv1,2,3,4,5 and DFv1,2. In addition, they determine the relative importance of the vibration-vibration and vibration-translation, rotation energy transfer pathways for v or 2 in both molecules. Applying these techniques at higher temperatures gives the self-relaxation rate constants between 300 and 700 K for HFv1-5. Using different partners permits the determination of the rate constants for collisional relaxation of HFv3,4,5 by H2, D2, CH4, CD4, and C02.
APPROVED FOR PUBLIC RELEASE