Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 13, Issue 18, Pages 8186-8194Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c0cp02515a
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Funding
- Consejo Superior de Investigaciones Cientificas (CSIC)
- Spanish Ministry of Science and Innovation (MCINN)
- MCINN [CSD2007-00013, CTQ2008-02578/BQU, FIS-2007-62002]
- Consolider program Science and Applications of Ultrafast Ultraintense Lasers'' [CSD2007-00013]
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The role of the conical intersection between the (1)Q(1) and (3)Q(0) excited states in the photodissociation of CH3I 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 P-2(3/2) state. The versatility of the slice imaging technique in combination with resonance enhanced multiphoton ionization (REMPI) detection of I(P-2(3/2)) atoms allow distinct measurements of the competing processes. The I(P-2(3/2)) atom kinetic energy distributions (KEDs) obtained in both cases reflect inverted vibrational progressions of the nu(2) 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.
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