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J. Phys. Chem. 1989, 93, 1267-1272 1267 Photoinduced Harpoon Reactions as a Probe of Condensed-Phase Dynamics: IC1 in
 

Summary: J. Phys. Chem. 1989, 93, 1267-1272 1267
Photoinduced Harpoon Reactions as a Probe of Condensed-Phase Dynamics: IC1 in
Liquid and Solid Xenon
F. Okada? L. Wiedeman, and V. A. Apkarian*
Department of Chemistry, University of California, Irvine, California 92717 (Received: May 1 I. 1988;
In Final Form: July 7, 1988)
Two-photon-induced harpoon reactions of IC1 in liquid and solid xenon are reported. The reaction dynamics is followed
by monitoring the luminescent products: the triatomic Xe2Cl and Xe21exciplexes. Action spectra and branching ratios
as a function of excitation energy are reported. The efficient production of the nonthermodynamic product, the iodide, in
the liquid phase implies that the cage exit of the ejected C1 atom is direct and sudden. The absenceof iodide in the crystalline
solids establishes the absenceof direct cage exit in the ordered phase. Line-shift.measurementsat the phase transition indicate
that the exciplexesare stronglyclustered in the liquid phase. The effect of clustering on dynamicsis the prevention of exchange
between iodide and chlorine-the solvent cage excludes C1 atoms. Branching ratios and action spectra are used to identify
the potential surfaces in the exit channel and the optical resonances in the entrance channel. The two-photon charge-transfer
excitations are enhanced by two-electron resonances that allow selectivityof products.
Introduction
Photoinduced harpoon reactions between molecular halogens
and rare-gas atoms, to produce the rare-gas halide exciplexes
proceed efficientlyin condensed media, in both and liquid&
rare gases. While the optical threshold of these processes is in

  

Source: Apkarian, V. Ara - Department of Chemistry, University of California, Irvine

 

Collections: Chemistry