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A mechanism for the quenching of I* in photodissociation of methyl iodide adsorbed on a MgO surface

✍ Scribed by Hua Guo; George C. Schatz

Publisher
Elsevier Science
Year
1991
Tongue
English
Weight
496 KB
Volume
184
Category
Article
ISSN
0009-2614

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✦ Synopsis

We report a timedependent wave packet study of non-adiabatic transitions in the photodissociatibn of methyl iodide adsorbed on a MgO surface. The dissociation dynamics is characterized using a twodegreeaf-freedom model in which the CH, group is replaced by an atom, and the CH91 is assumed to be perpendicular to the surface with CHs either up or down. The surface is taken to be rigid. Two coupled, excited, potential surfaces, correlating to I and I*, were used. When CH, is up, the dissociation dynamics is very similar to that in the gas phase. When CHI is down, chattering of the CHp between I and the surface results in an important second crossing of the intersection between the two excited surfaces, leading to partial quenching of the excited iodine atom. This result provides one possible mechanism for recent surface experiments in which the I* yield was found to be lower than in gas phase CHXI dissociation.

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