Kinetics of intramolecular carbon atom exchange in ketene

Journal Article · Sun Sep 15 04:00:00 EDT 1991 · Journal of Chemical Physics; (United States)

DOI:https://doi.org/10.1063/1.460764· OSTI ID:5332936

Lovejoy, E R; Kim, S K; Alvarez, R A; Moore, C B ^[1]

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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

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400202* -- Isotope Effects
Isotope Exchange
& Isotope Separation
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
DISSOCIATION
ENERGY LEVELS
EXCITED STATES
ISOMERIZATION
ISOTOPIC EXCHANGE
KETENES
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
VIBRATIONAL STATES
YIELDS