Bond-breaking in CCl4via dissociative electron attachment (DEA) has been studied using a velocity map imaging (VMI) spectrometer. A number of effects related to the dissociation dynamics have been revealed. The near-zero eV s-wave electron attachment, which leads to the production of Cl- anions, is accompanied by a very efficient intramolecular vibrational redistribution. This is manifested by a small fraction of the excess energy being released in the form of the fragments' translation energy. A similar effect is observed for higher-lying electronic resonances with one exception: the resonance centered around 6.2 eV leads to the production of fast Cl2- fragments and their angular distribution is forward peaking. This behavior could not be explained with a single-electronic-state model in the axial recoil approximation and is most probably caused by bending dynamics initiated by a Jahn-Teller distortion of the transient anion. The CCl2- fragment has a reverse backward-peaking angular distribution, suggesting the presence of a long-distance electron hopping mechanism between the fragments.

Center for Atomic Molecular and Optical Sciences and Technologies Joint Initiative of IIT Tirupati and IISER Tirupati Yerpedu 517619 Andhra Pradesh India

Chemical Sciences Division Lawrence Berkeley National Laboratory Berkeley CA 94720 USA

Indian Institute of Science Education and Research Kolkata Mohanpur 741246 India

J Heyrovský Institute of Physical Chemistry Czech Academy of Sciences 182 23 Dolejškova 2155 3 Prague Czech Republic

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