INFRARED SPECTRA OF MATRIX ISOLATED HYDROGEN FLUORIDE AND VIBRATIONAL PREDISSOCIATION OF THE DIMER

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1983

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Ohio State University

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Infrared spectra are reported for HF species and their deuterated isotopomers isolated in solid Ar, $N_{2},$ and CO and in various binary mixed matrices. HF stretching and FH...F bending fundamentals are observed for several dimer isotopomers. The HF molecule forms appreciable hydrogen bonds with CO and $H_{2}O$, and HF stretching frequencies are repoprted for the Ar-isolation bimolecules FH...X, with X=Kr, Xe, $N_{2},$ CO, and $H_{2}O.$ The Ar matrix isolation data are compared with the vapor phase infrared absorption data and the laser-induced vibrational predissociation data, and values are proposed for all six fundamental frequencies of the dimer. In an attempt to reconcile the various observations, our analysis also includes a predissociation lifetime correlation suggested to us by current theory. It makes use of the vibrational predissociation lifetime ranges reported for bands in the HF stretching region. The proposed interpretation suggests a low picosecond timescale for vibrational predissociation of the $\nu_{2}$ state, with longer lifetimes associated with proposed $\nu_{1},$ and $\nu_{2},$ + $\nu_{5},$ states. The observed lifetime ranges correlate with the relative translational energies of the product monomers when it is assumed that the excitation energy quickly accesses similer incipient vibrational predissociation channels from any of the initially excited vibrations.

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Author Institution: Department of Chemistery, Taxas Tech University

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