Journal
CHEMICAL PHYSICS LETTERS
Volume 368, Issue 3-4, Pages 324-330Publisher
ELSEVIER SCIENCE BV
DOI: 10.1016/S0009-2614(02)01882-1
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The dependence of the I(P-2(3/2))/I(P-2(1/2)) branching ratio on the end-over-end rotational state of the methyl photo-fragment, CH3 (nu(2) = 2\N, K = 1), after photodissociation at 266 nm of single quantum state-selected CH3I (JK = 11) molecules is reported. Using velocity map imaging the spatial velocity distribution of the vibrationally excited CH3 (nu(2) = 2) photoftagment was detected. The I(P-2(3/2)) and I(P-2(1/2)) yields were extracted from the speed distribution of rotationally selected CH3 (nu(2) = 2\N, K = 1) photofragments. Quantitative analysis shows a strongly increasing I(P-2(3/2))/I(P-2(1/2)) branching ratio with increasing CH3 end-over-end rotational motion, in reasonable agreement with recent three-dimensional state-to-state ab initio calculations. (C) 2002 Elsevier Science B.V. All rights reserved.
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