Photodissociation of laboratory oriented molecules: Revealing molecular frame properties of nonaxial recoil

A.J. van den Brom, T.P. Rakitzis, M.H.M. Janssen

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    We report the photodissociation of laboratory oriented OCS molecules. A molecular beam of OCS molecules is hexapole state-selected and spatially oriented in the electric field of a velocity map imaging lens. The oriented OCS molecules are dissociated at 230 nm with the linear polarization set at 45° to the orientation direction of the OCS molecules. The CO(ν=0,J) photofragments are quantum state-selectively ionized by the same 230 nm pulse and the angular distribution is measured using the velocity map imaging technique. The observed CO(ν=0,J) images are strongly asymmetric and the degree of asymmetry varies with the CO rotational state J. From the observed asymmetry in the laboratory frame we can directly extract the molecular frame angles between the final photofragment recoil velocity and the permanent dipole moment and the transition dipole moment. The data for CO fragments with high rotational excitation reveal that the dissociation dynamics is highly nonaxial, even though conventional wisdom suggests that the nearly limiting β parameter results from fast axial recoil dynamics. From our data we can extract the relative contribution of parallel and perpendicular transitions at 230 nm excitation. © 2004 American Institute of Physics.
    Original languageEnglish
    Pages (from-to)11645-52
    JournalJournal of Chemical Physics
    Issue number23
    Publication statusPublished - 2004


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