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Title: Predicting the effect of angular momentum on the dissociation dynamics of highly rotationally excited radical intermediates

We present a model which accurately predicts the net speed distributions of products resulting from the unimolecular decomposition of rotationally excited radicals. The radicals are produced photolytically from a halogenated precursor under collision-free conditions so they are not in a thermal distribution of rotational states. The accuracy relies on the radical dissociating with negligible energetic barrier beyond the endoergicity. We test the model predictions using previous velocity map imaging and crossed laser-molecular beam scattering experiments that photolytically generated rotationally excited CD{sub 2}CD{sub 2}OH and C{sub 3}H{sub 6}OH radicals from brominated precursors; some of those radicals then undergo further dissociation to CD{sub 2}CD{sub 2} + OH and C{sub 3}H{sub 6} + OH, respectively. We model the rotational trajectories of these radicals, with high vibrational and rotational energy, first near their equilibrium geometry, and then by projecting each point during the rotation to the transition state (continuing the rotational dynamics at that geometry). This allows us to accurately predict the recoil velocity imparted in the subsequent dissociation of the radical by calculating the tangential velocities of the CD{sub 2}CD{sub 2}/C{sub 3}H{sub 6} and OH fragments at the transition state. The model also gives a prediction for the distribution of angles between themore » dissociation fragments’ velocity vectors and the initial radical’s velocity vector. These results are used to generate fits to the previously measured time-of-flight distributions of the dissociation fragments; the fits are excellent. The results demonstrate the importance of considering the precession of the angular velocity vector for a rotating radical. We also show that if the initial angular momentum of the rotating radical lies nearly parallel to a principal axis, the very narrow range of tangential velocities predicted by this model must be convoluted with a J = 0 recoil velocity distribution to achieve a good result. The model relies on measuring the kinetic energy release when the halogenated precursor is photodissociated via a repulsive excited state but does not include any adjustable parameters. Even when different conformers of the photolytic precursor are populated, weighting the prediction by a thermal conformer population gives an accurate prediction for the relative velocity vectors of the fragments from the highly rotationally excited radical intermediates.« less
Authors:
;  [1]
  1. Department of Chemistry and the James Franck Institute, The University of Chicago, Chicago, Illinois 60637 (United States)
Publication Date:
OSTI Identifier:
22416069
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 5; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANGULAR MOMENTUM; ANGULAR VELOCITY; DECOMPOSITION; DISSOCIATION; EQUILIBRIUM; KINETIC ENERGY; LASER RADIATION; MOLECULAR BEAMS; PRECURSOR; PROPYLENE; RADICALS; RECOILS; ROTATION; ROTATIONAL STATES; TIME-OF-FLIGHT METHOD