Kaye, Jack A. and Kuppermann, Aron (1986) Collinear quasiclassical trajectory study of collision-induced dissociation on a model potential energy surface. Journal of Chemical Physics, 84 (3). pp. 1463-1476. ISSN 0021-9606 http://resolver.caltech.edu/CaltechAUTHORS:KAYjcp86
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Quasiclassical trajectory calculations have been carried out at energies above the threshold for collision-induced dissociation for a model symmetric collinear atom–diatomic molecule system. Exact quantum mechanical calculations have shown that quasiclassical trajectories give a qualitatively correct picture of the dynamics in this system, in so far as reaction and total dissociation probabilities are concerned. Trajectories leading to dissociation are found to lie almost entirely in well-defined reactivity bands, with the exception of a few occurring in a small chattering region in which the outcome of the trajectory is extremely sensitive to its initial conditions. The energy distribution functions of the dissociated atoms are obtained and shown to vary substantially with initial conditions (reagent vibrational and translation energy). The form of these distributions is, to a major extent, determined by the position and width of the reactivity bands. The different dissociation reactivity bands are shown to be associated with different types of trajectories. Part of the vibrational enhancement of dissociation arises from the fact that the simplest possible trajectory leading to dissociation (one which crosses the symmetric stretch line only once prior to the onset of dissociation) is not obtained with ground state reagents.
|Additional Information:||© 1986 American Institute of Physics. Received 29 March 1985; accepted 10 October 1985. The calculations reported here were performed on the Dreyfus-NSF Theoretical Chemistry Computer which was funded through grants from the Camille and Henry Dreyfus Foundation, the National Science Foundation (Grant No. CHE-78-20235), and the Sloan Fund of the California Institute of Technology. This work was supported in part by a contract (No. F49620-79-C-0187) from Air Force Office of Scientific Research. Work performed [by J.A.K.] in partial fulfillment of the requirements for the Ph.D. degree in Chemistry at the California Institute of Technology. Arthur Amos Noyes Laboratory of Chemical Physics, Contribution No. 7011.|
|Subject Keywords:||ATOM−MOLECULE COLLISIONS, DIATOMIC MOLECULES, DISSOCIATION, POTENTIAL ENERGY, QUANTUM MECHANICS, CHEMICAL REACTION KINETICS|
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|Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Tony Diaz|
|Deposited On:||22 Oct 2008 17:13|
|Last Modified:||26 Dec 2012 10:25|
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