A b i n i t i o potential energy surfaces and trajectory studies of A-band photodissociation dynamics: CH3I*→CH3+I and CH3+I*

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Abstract
A b initio contracted spin–orbit configuration interaction (SOCI) calculations have been carried out to obtain potential energy surfaces of 3Q0 and 1Q1 excited states of methyl iodide as functions of all the geometrical parameters except for the three C–H stretches. The results are fitted to six-dimensional diabatic potential functions and their couplings. Classical trajectory calculations have been performed using these potential functions. The rotation of the CH3 product in the I channel has been calculated to be perpendicular to the top axis and to have a peak at N=5 and extend up to N=8, whereas it is cold in the I* channel, in good agreement with recent experiments. The CH3 rotation is excited by the time trajectories arrive at the conical intersection region; this excitation is retained in the I-channel product because the 1Q1 surface has a small bending force constant outside the conical intersection, whereas it is damped in the I* channel because 3Q0 still has a large bending force constant. The calculated distribution in the ν2 umbrella vibrational mode of the CH3 product is hot and has a peak at v=2 for the I channel, and is cool for the I* channel, in good agreement with recent experiments. This channel selectivity is due to the difference in the preferred structure of the CH3 group outside the conical intersection region; while the 3Q0 surface prefers a bent CH3 until the CH3–I distance becomes very large, 1Q1 wants a planar CH3. The location of conical intersection and the ground-excited energy difference there are in good agreement with those deduced from experiment if a dynamical effect is taken into account.