Photodissociation of the propargyl and propynyl (C{sub 3}D{sub 3}) radicals at 248 and 193 nm

Journal Article · Wed Jan 28 04:00:00 EST 2009 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.3067705· OSTI ID:21255527

Crider, Paul E; Castiglioni, Luca; Kautzman, Kathryn E; Neumark, Daniel M ^[1]

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1. Department of Chemistry, University of California, Berkeley, California 94720 (United States) and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)

The photodissociation of perdeuterated propargyl (D{sub 2}CCCD) and propynyl (D{sub 3}CCC) radicals was investigated using fast beam photofragment translational spectroscopy. Radicals were produced from their respective anions by photodetachment at 540 and 450 nm (below and above the electron affinity of propynyl). The radicals were then photodissociated at 248 or 193 nm. The recoiling photofragments were detected in coincidence with a time- and position-sensitive detector. Three channels were observed: D{sub 2} loss, CD+C{sub 2}D{sub 2}, and CD{sub 3}+C{sub 2}. Observation of the D loss channel was incompatible with this experiment and was not attempted. Our translational energy distributions for D{sub 2} loss peaked at nonzero translational energy, consistent with ground state dissociation over small (<1 eV) exit barriers with respect to separated products. Translational energy distributions for the two heavy channels peaked near zero kinetic energy, indicating dissociation on the ground state in the absence of exit barriers.

• OSTI ID: 21255527
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 4 Vol. 130; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ANIONS
DISSOCIATION
ELECTRON DETACHMENT
ENERGY SPECTRA
GROUND STATES
KINETIC ENERGY
MILLI EV RANGE
ORGANIC COMPOUNDS
PHOTOLYSIS
POSITION SENSITIVE DETECTORS
RADICALS
REACTION KINETICS
SPECTROSCOPY