A 4D wave packet study of the CH 3 I photodissociation in the A band. Comparison with femtosecond velocity map imaging experiments A. García-Vela 1, R. de Nalda 2, J. Durá 3, J. González-Vázquez 2,3, and L. Bañares 3 1 Instituto de Física Fundamental, Consejo Superior de Investigaciones Científicas, Serrano 123, Madrid, Spain 2 Instituto de Química Física Rocasolano, Consejo Superior de Investigaciones Científicas, Serrano 123, Madrid, Spain 3 Departamento de Química Física I, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, Madrid, Spain Good agreement is found between experiment and the 4D theoretical model for the properties Involving the I* channel and the ground vibrational level of the umbrella mode in the I dissociation channel. Such a good agreement (which improves that of the previous 3D description) is mainly due to the averaging of the calculated magnitudes over the spectral bandwidth of the pump pulse (in addition to the probe pulse) carried out in the present model, since it describes better the experimental conditions. In this sense, 3D simulations carried out in the same conditions give very similar results to the 4D ones, indicating a small influence of the symmetric stretch mode in the dynamics. Disagreement between theory and experiment is still found, however, for the properties corresponding to the vibrational excitations of the CH 3 fragment (for both the umbrella and the symmetric stretch mode) in the I dissociation channel. Introduction: The photodissociation of methyl iodide in the A band (λ=267 nm) has been studied both experimentally and theoretically [1]. Femtosecond pump-probe experiments in combination with velocity map imaging were carried out to measure the relative reaction times (clocking) of the different photodissociation channels. Multisurface nonadiabatic wave packet calculations in 3D were also previously performed using the best ab initio potential surfaces, nonadiabatic coupling, and transition dipole moments currently available [2-4]. Good general agreement was found between experiment and theory except for the channels involving excitation of the umbrella mode of the CH 3 fragment [1]. New, more accurate absolute reaction times have been recently measured for the different dissociation channels, and improved multisurface wave packet calculations including 4 degrees of freedom have been recently carried out. Both the new experiments and simulations are reported in the present work. Conclusions: After applying a 4D quantum dynamical model to describe the CH 3 I photodissociation the discrepancies with the experimental data still remain regarding the properties related to the I dissociation channel when the CH 3 fragment is vibrationally excited. The results indicate that such a discrepancy is not due to a dynamical effect or to poor description of the model because of its reduced dimensionality nature. We suspect that the discrepancy is rather due to an effect caused by the experimental fragment detection process, which is not modeled in the theory. References [1] R. de Nalda, J. Durá, A. García-Vela, J. G. Izquierdo, J. González-Vázquez, and L. Bañares, J. Chem. Phys. 128, (2008). [2] D. Xie, H. Guo, Y. Amatatsu, and R. Kosloff, J. Phys. Chem. A 104, 1009 (2000). [3] A. B. Alekseyev, H.-P. Liebermann, R. J. Buenker, and S. N. Yurchenko, J. Chem. Phys. 126, (2007). [4] A.B. Alekseyev, H.-P. Liebermann, and R.J. Buenker, J.Chem. Phys. 126, (2007). Acknowledgements: Ministerio de Ciencia e Innovación, Spain, Grants No. CTQ C02-01 and FIS , the Consolider program, Grant No. CSD , and the Centro de Supercomputación de Galicia (CESGA). Femtosecond laser pump + resonant probe combined with velocity-map ion imaging velocity-map imaging radius kinetic energy (ion lens + 2D detection ) A.T. J.B. Eppink and D.H. Parker, Rev. Sci. Instrum. 68, 3477 (1997) Initial excitation to A-band with 267 nm Resonant probing of CH 3 fragment causing a 2+1 REMPI process Velocity-map ion imaging of CH 3 +. The speed and angular distributions contain detailed information of the multichannel bond-breaking Ultrashort pump and probe pulses process De Nalda et al., J. Chem. Phys. 128, (2008) CH 3 I A-band: clocking experiment Abel inverted CH 3 + images Multisurface wave packet treatment in 4D Differences between previous 3D and present 4D simulations 4D: -- Inclusion of the C-H stretch mode -- Calculated magnitudes are averaged over the spectral bandwidth of both the pump and the probe pulses -- Initial pumping to both the 3 Q 0 and 1 Q 1 excited states 3D: -- Calculated magnitudes are averaged over the spectral bandwidth of only the probe pulse -- Initial pumping only to the 3 Q 0 excited state