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(Physical Chemistry Chemical Physics, 2011) Rubio-Lago, Luis; Rodríguez. Javier; García-Vela, Alberto; González, María; Amaral, Gabriel; Bañares Morcillo, Luis
The role of the conical intersection between the 1Q1 and 3Q0 excited states in the photodissociation of CH3I at 304 nm is investigated drawing a comparison between the adiabatic—through direct absorption to the 3Q1 state—and non-adiabatic—via the 1Q1 → 3Q0 conical intersection—production of I atoms in the ground 2P3/2 state. The versatility of the slice imaging technique in combination with resonance enhanced multiphoton ionization (REMPI) detection of I(2P3/2) atoms allow distinct measurements of the competing processes. The I(2P3/2) atom kinetic energy distributions (KEDs) obtained in both cases reflect inverted vibrational progressions of the ν2 umbrella mode of the CH3 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