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Kinetics of intramolecular carbon atom exchange in ketene

Journal Article · · Journal of Chemical Physics; (United States)
DOI:https://doi.org/10.1063/1.460764· OSTI ID:5332936
; ; ;  [1]
  1. Department of Chemistry, University of California at Berkeley, and Materials and Chemical Sciences Division of the Lawrence Berkeley Laboratory, Berkeley, California (USA)

Intramolecular carbon atom exchange in highly vibrationally excited ketene was studied by monitoring the carbon monoxide fragments ({sup 12}CO and {sup 13}CO ) from the photodissociation of {sup 12}CH{sub 2}{sup 13}CO and {sup 13}CH{sub 2}{sup 12}CO. Two experimental techniques were employed. In one set of experiments the IR transient absorptions of {sup 12}CO and {sup 13}CO were measured following pulsed excimer excitation of ketene {sup 13}C isotopomers, giving carbon atom exchange yields at 351 and 308 nm in a low pressure gas cell. In the other set of experiments, jet-cooled ketene {sup 13}C isotopomers were excited with tunable near-UV radiation, and the CO products were detected by monitoring their VUV laser-induced fluorescence. Carbon atom exchange yields were measured for energies extending from below the triplet decomposition threshold (CH{sub 2}CO{r arrow}CH{sub 2}({ital X} {sup 3}B{sub 1})+CO({ital X} {sup 1}{Sigma}{sup +})) to about 4000 cm{sup {minus}1} above the singlet threshold (CH{sub 2}CO{r arrow}CH{sub 2}({ital a} {sup 1}{ital A}{sub 1})+CO({ital X} {sup 1}{Sigma}{sup +})).

DOE Contract Number:
AC03-76SF00098
OSTI ID:
5332936
Journal Information:
Journal of Chemical Physics; (United States), Journal Name: Journal of Chemical Physics; (United States) Vol. 95:6; ISSN JCPSA; ISSN 0021-9606
Country of Publication:
United States
Language:
English