Two‐Photon Photoassisted Reactions of Collision Pairs Consisting of Xe with Halogen‐Containing Polyatomic Molecules

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Abstract
Excitation spectra have been acquired for the two‐photon, laser‐assisted reactions between collision pairs of Xe with CCl4, CCl1Br, CH3I, CH2I2, CH2ICl, and SOCl2. In each case the product of the reaction is XeX(B,C); X = halogen. The excitation spectra obtained at 300 K in 100 Torr of Xe and 1.3 Torr of reagent have thresholds near 255 nm and increase toward shorter wavelength. Unexpected resonance‐like features have been found in the excitation spectra of Xe/CH2ICl and Xe/CCl3Br. A set of relative two‐photon excitation rates was obtained at 238 and 227 nm for all pairs by comparison to CCl4, which was selected as a standard. The excitation spectra for the polyatomic molecular pairs can be compared to previously published excitation spectra of diatomic halogen molecules with Xe. The two‐photon, laser‐assisted reaction of the Xe·F2 van der Waals molecule prepared by free‐jet expansion also is reported.