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The time-resolved photodissociation dynamics of CH3I in the A-band has been studied theoretically using a wave packet model including four degrees of freedom, namely the C–I dissociation coordinate, the I–CH3 bending mode, the CH3 umbrella mode, and the C−H symmetric stretch mode. Clocking times and final product state distributions of the different dissociation (nonadiabatic) channels yielding spin-orbit ground and excited states of the I fragment and vibrationless and vibrationally excited (symmetric stretch ν1 and umbrella ν2 modes) CH3 fragments have been obtained and compared with the results of femtosecond velocity map imaging experiments. The wave packet calculations are able to reproduce with very good agreement the experimental reaction times for the CH3(ν1, ν2)+I*(2P1/2) dissociation channels with ν1 = 0 and ν2 = 0,1,2, and also for the channel CH3(ν1 = 0, ν2 = 0)+I(2P3/2). However, the model fails to predict the experimental clocking times for the CH3(ν1, ν2)+I(2P3/2) channels with (ν1, ν2) = (0, 1), (0, 2), and (1, 0), that is, when the CH3 fragment produced along with spin-orbit ground state I atoms is vibrationally excited. These results are similar to those previously obtained with a three-dimensional wave packet model, whose validity is discussed in the light of the results of the four-dimensional treatment. Possible explanations for the disagreements found between theory and experiment are also discussed.
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