PHOTODISSOCIATION OF VIBRATIONALLY EXCITED $CH_{3}Cl$: MODIFICATION OF THE DISSOCIATION DYNAMICS
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Date
1997
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Ohio State University
Abstract
Vibrationally excited $CH_{3}Cl$ is prepared by laser excitation in the fourth overtone C-H stretch band near 725 nm photodissociated al fixed wavelengths near 240 nm which also probe either The H, Cl(${^{2}}P_{3/2}$), or Cl(${^{2}}P_{1/2}$) photofragments via (2+1) resonance enhanced multiphoton ionization (REMPI) in a time-of-flight mass spectrometer. Jet cooling of the $CH_{3}Cl$ reveals two partially resolved bands in the overtone excitation spectrum which are assigned to [5,0,0] and $[4,0,0] + 2\nu_{2}$. The product yields from the photolysis of vibrationally excited $CH_{3}Cl$ show decided enhancement compared to photolysis of the ground state. Branching ratios of atomic products are also determined for photolysis of both excited and ground state $CH_{3}Cl$. The ratio of Cl(${^{2}}P_{1/2}$) to Cl(${^{2}}P_{3/2}$) is dramatically larger for photolysis of vibrationally excited vs. ground state $CH_{3}Cl$.
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Author Institution: Department of Chemistry, The Johns Hopkins University