Doppler profiles and fine-structure branching ratios of O(3Pj) from photodissociation of carbon dioxide at 157 nm

Matsumi, Yutaka; Shafer, Neil; Tonokura, Kenichi; Kawasaki, Masahiro; Huang, Yu-Lin; Gordon, Robert J.
November 1991
Journal of Chemical Physics;11/15/1991, Vol. 95 Issue 10, p7311
Academic Journal
The O(2p 3Pj) (j=2, 1, and 0) fragments produced in the 157 nm photodissociation of CO2 were detected by resonance-enhanced multiphoton ionization in a molecular beam. The Doppler profiles and fine-structure branching ratios were measured for the oxygen-atom photofragment in the 3Pj states. The Doppler profiles were analyzed to give an anisotropy parameter of β=2.0±0.2 and an internal energy equivalent to 3.9±0.3 vibrational quanta of CO. The fine-structure populations were found to be 0.70±0.05, 0.16±0.03, and 0.14±0.03 (with error bars of ±σ) for j=2, 1, and 0, respectively. A mechanism is proposed in which complex on the 1B2 surface undergoes intersystem crossing to the 3B2 surface. A phase-space model with a constraint on the impact parameter is shown to be consistent with the observed energy release. The nonstatistical fine-structure population could be caused by long-range interactions on the triplet surface. In a bulb experiment, O(3P) was produced by quenching of O(1D). The fine-structure populations of the resulting O(3Pj) were 0.64±0.04, 0.25±0.04, and 0.11±0.04. This state distribution is consistent with a long-lived complex which decays to give statistical products.


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