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A quantum and semiclassical study of dynamical resonances in the C + NO-->CN + O reaction

Abrol, Ravinder and Wiesenfeld, Laurent and Lambert, Bruce and Kuppermann, Aron (2001) A quantum and semiclassical study of dynamical resonances in the C + NO-->CN + O reaction. Journal of Chemical Physics, 114 (17). pp. 7461-7470. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:ABRjcp01a

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Abstract

Accurate quantum mechanical reactive scattering calculations were performed for the collinear C+NO-->CN+O reaction using a polynomial-modified London Eyring Polanyi Sato (PQLEPS) potential energy surface (PES), which has a 4.26 eV deep well in the strong interaction region, and a reference LEPS PES, which has no well in that region. The reaction probabilities obtained for both PESs show signatures for resonances. These resonances were characterized by calculating the eigenvalues and eigenvectors of the collision lifetime matrix as a function of energy. Many resonances were found for scattering on both PESs, indicating that the potential well in the PQLEPS PES does not play the sole role in producing resonances in this relatively heavy atom system and that Feshbach processes occur for both PESs. However, the well in the PQLEPS PES is responsible for the differences in the energies, lifetimes, and compositions of the corresponding resonance states. These resonances are also interpreted in terms of simple periodic orbits supported by both PESs (using the WKB formalism), to further illustrate the role played by that potential well on the dynamics of this reaction. The existence of the resonances is associated with the dynamics of the long-lived CNO complex, which is much different than that of systems having an activation barrier. Although these results were obtained for a collinear model of the reaction, its collinearly-dominated nature suggests that related resonant behavior may occur in the real world.


Item Type:Article
Additional Information:©2001 American Institute of Physics. Received: 23 August 2000; accepted: 19 December 2000 One of us (L.W.) thanks Caltech for its welcome and support during the 1999–2000 academic year. This work has been supported in part by NSF Grant No. CHE 9810050 and by a joint NSF/CNRS Grant No. INT-9910196. The Laboratoire de Spectrométrie Physique is a joint CNRS/Université Joseph-Fourier laboratory, under the name UMR 5580.
Subject Keywords:carbon; nitrogen compounds; atom-molecule reactions; reaction kinetics; eigenvalues and eigenfunctions; potential energy surfaces; matrix algebra; WKB calculations
Record Number:CaltechAUTHORS:ABRjcp01a
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:ABRjcp01a
Alternative URL:http://dx.doi.org/10.1063/1.1349083
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:1143
Collection:CaltechAUTHORS
Deposited By: Archive Administrator
Deposited On:22 Dec 2005
Last Modified:26 Dec 2012 08:42

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