Abstract

The role of the conical intersection between the (1)Q(1) and (3)Q(0) excited states in the photodissociation of CH(3)I at 304 nm is investigated drawing a comparison between the adiabatic--through direct absorption to the (3)Q(1) state--and non-adiabatic--via the (1)Q(1)→(3)Q(0) conical intersection--production of I atoms in the ground (2)P(3/2) state. The versatility of the slice imaging technique in combination with resonance enhanced multiphoton ionization (REMPI) detection of I((2)P(3/2)) atoms allow distinct measurements of the competing processes. The I((2)P(3/2)) atom kinetic energy distributions (KEDs) obtained in both cases reflect inverted vibrational progressions of the ν(2) umbrella mode of the CH(3) co-product. The experimental results show a satisfactory agreement with multisurface wave packet calculations using a reduced dimensionality (pseudotriatomic) model carried out on the available ab initio potential energy surfaces.

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