ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
Applying the two-photon laser-induced fluorescence technique for nascent state resolved ClO(X 2ΠΩ,v,J) detection, the photofragmentation dynamics of OClO in the (A˜ 2A211,0,0) and the (A˜ 2A218,0,0) state is investigated at fixed photolysis wavelengths of 351 nm and 308 nm. In both experiments the product fragments are formed in their electronic ground states, namely ClO(2ΠΩ) and O(3P). A complete product state analysis proves the ClO radicals originating from the OClO(A˜ 2A211,0,0) dissociation at 351 nm to be formed in v=0–4 vibrational states with a spin–orbit ratio of P(2Π3/2):P(2Π1/2)=3.8±0.5. The ClO fragment shows moderate rotational excitation. The obtained ClO product state distributions and the relatively high translational energy of the fragments can be explained by predissociation of the (A˜ 2A2ν1,0,0)-excited parent molecule in the course of which the initial symmetric stretch motion (ν1) of OClO is transferred into the dissociative asymmetric stretching mode (ν3). ClO line profile measurements indicate a dissociation time of less than 0.5 ps. Resulting from the OClO(A˜ 2A218,0,0) dissociation at 308 nm ClO is generated in very high vibrational states. The rotational excitation is comparable to that of the 351 nm photolysis study. © 1996 American Institute of Physics.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.471649
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