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A detailed experimental and theoretical study of the femtosecond A -band photodissociation of C H3I

AutorNalda, R. de; Durá, J. ; García Vela, Alberto ; Izquierdo, J.G.; González Vázquez, J.; Bañares, L.
Fecha de publicación2008
EditorAmerican Institute of Physics
CitaciónJournal of Chemical Physics 128: 244309 (2008)
ResumenThe real time photodissociation dynamics of C H3I from the A band has been studied experimentally and theoretically. Femtosecond pump-probe experiments in combination with velocity map imaging have been carried out to measure the reaction times (clocking) of the different (nonadiabatic) channels of this photodissociation reaction yielding ground and spin-orbit excited states of the I fragment and vibrationless and vibrationally excited (symmetric stretch and umbrella modes) C H3 fragments. The measured reaction times have been rationalized by means of a wave packet calculation on the available ab initio potential energy surfaces for the system using a reduced dimensionality model. A 40 fs delay time has been found experimentally between the channels yielding vibrationless CH3(ν=0) and I(2P3/2) and I*(2P1/2) that is well reproduced by the calculations. However, the observed reduction in delay time between the I and I* channels when the C H3 fragment appears with one or two quanta of vibrational excitation in the umbrella mode is not well accounted for by the theoretical model. © 2008 American Institute of Physics.
URIhttp://hdl.handle.net/10261/79397
DOI10.1063/1.2943198
Identificadoresdoi: 10.1063/1.2943198
issn: 0021-9606
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