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Title: Photofragment imaging: The 266-nm photolysis of CD sub 3 I

Journal Article · · Journal of Physical Chemistry; (USA)
DOI:https://doi.org/10.1021/j100375a017· OSTI ID:6329411
 [1];  [2];  [3];  [4];  [5];  [6]
  1. Sandia National Laboratories, Livermore, CA (USA)
  2. Catholic Univ. of Nijmegen (Netherlands)
  3. Free Univ., Amsterdam (Netherlands)
  4. Univ. of Arizona, Tucson (USA)
  5. Williams College, Williamstown, MA (USA)
  6. Univ. of California, Santa Cruz (USA)

Internal state and velocity distributions of methyl fragments from the 266-nm photodissociation of CD{sub 3}I in a supersonic beam are measured by using photofragment imaging. Methyl radicals are state-selectively ionized by using (2+1) resonance-enhanced multiphoton ionization (REMPI) via the 3p{sub z} Rydberg state, and the imaging technique records the velocity distribution of the ions. A line-by-line rotational analysis of the 3p{sub z}{l arrow}{tilde X} 0{sup 0}{sub 0} band, including conservation of the parent molecule's ortho:para ratio in the planar fragment molecules, indicates that about 90 cm{sup {minus}1} of rotational excitation about a C{sub 2} axis in CD{sub 3} results from the photolysis. The photodissociation appears to conserve the initial (low) rotational excitation about the C{sub 3} axis of the (cold) parent molecule. From the previously derived 3p{sub z}-{tilde X} Franck-Condon factors the branching ratio for the v = 2/v = 0 levels of the umbrella mode is determined to be 1.15 {plus minus} 0.13.

OSTI ID:
6329411
Journal Information:
Journal of Physical Chemistry; (USA), Vol. 94:12; ISSN 0022-3654
Country of Publication:
United States
Language:
English