ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
CCl2 free radicals were produced by a pulsed dc discharge of CCl4 (in Ar). Ground electronic state CCl2(X˜) radical was electronically excited to A˜ 1B1(0,4,0) vibronic state by Nd:YAG laser pumped dye laser at 541.52 nm. The laser induced fluorescence signal is observed to be a monoexponential decay curve corresponding to the decay of the A˜ state under supersonic jet conditions and the lifetime of CCl2(A˜→X˜) transition was measured being 0.83±0.03 μs. Experimental quenching data of excited CCl2(A˜ 1B1 and a˜ 3B1) by alkanes were obtained by observing the time-resolved total fluorescence signal of the excited CCl2 radical in a cell, which showed a superposition of two exponential components under the presence of a quencher. The quenching rate constants of A˜(1B1) and a˜(3B1) states of CCl2, KA, and Ka, were derived by analyzing the experimental data according to a proposed three-level model to deal with the CCl2(X˜ 1A1,A˜ 1B1,a˜ 3B1) system. KA and Ka increase steadily by increasing the number of C–H bonds contained in the alkane molecules. The formation cross sections of the complexes of electronically excited CCl2 radicals and alkane molecules were calculated by means of a collision complex model. It is shown that the dependence of the formation cross section of the complex on the number of C–H bonds contained in the alkane molecule is in agreement with that of the measured quenching cross section. © 2001 American Institute of Physics.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.1377029
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