Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 123, Issue 31, Pages 7638-7645Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja0102843
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We present semiclassical simulations of the dynamical events which follow the n --> pi* excitation of an azomethane molecule: decay to the ground state, isomerization, and dissociation. Ab initio potential energy surfaces and couplings, slightly modified according to available experimental data, are employed in conjunction with a trajectory-surface-bopping method. For an isolated molecule, we show that dissociation takes place in the ground state, because the radiationless decay is very fast. The dissociation is mainly sequential: the methyldiazenyl radical first produced fragmentates very rapidly to N-2 + CH3.. The results of previous experiments by Lee's and Zewail's groups, from which partially conflicting conclusions had been drawn, are reproduced and interpreted. Molecular dynamics, coupled to the surface-hopping algorithm, allows us to simulate the photochemistry in acqueous solution. Here the fragmentation is suppressed because of vibrational energy loss to the solvent: only the isomerization takes place.
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