Sims, I. R. and Gruebele, M. and Potter, E. D. and Zewail, A. H. (1992) Femtosecond real-time probing of reactions. VIII. The bimolecular reaction Br+I2. Journal of Chemical Physics, 97 (6). pp. 4127-4148. ISSN 0021-9606. doi:10.1063/1.463917. https://resolver.caltech.edu/CaltechAUTHORS:SIMjcp92
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Abstract
In this paper, we discuss the experimental technique for real-time measurement of the lifetimes of the collision complex of bimolecular reactions. An application to the atom–molecule Br+I_2 reaction at two collision energies is made. Building on our earlier Communication [J. Chem. Phys. 95, 7763 (1991)], we report on the observed transients and lifetimes for the collision complex, the nature of the transition state, and the dynamics near threshold. Classical trajectory calculations provide a framework for deriving the global nature of the reactive potential energy surface, and for discussing the real-time, scattering, and asymptotic (product-state distribution) aspects of the dynamics. These experimental and theoretical results are compared with the extensive array of kinetic, crossed beam, and theoretical studies found in the literature for halogen radical–halogen molecule exchange reactions.
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| Additional Information: | © 1992 American Institute of Physics. Received 13 February 1992; accepted 8 June 1992. This work was supported by a grant from the National Science Foundation. We are grateful for the very helpful discussions we have had with Professor D. Herschbach and Professor M. Okumura, and would like to thank Professor J.D. McDonald for providing additional information on the original scattering experiments done at Harvard (Ref. 16). [I.R.S. was an] SERC-NATO post-doctoral fellow from UK. Arthur Amos Noyes Laboratory of Chemical Physics, Contribution No. 8576. | |||||||||
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| Subject Keywords: | REAL TIME SYSTEMS, LIFETIME, BROMINE COMPLEXES, IODINE COMPLEXES, CHEMICAL REACTIONS, BROMINE, IODINE MOLECULES, ATOM−MOLECULE COLLISIONS, TRANSIENTS, THRESHOLD ENERGY, TRAJECTORIES, CLASSICAL MECHANICS, POTENTIAL ENERGY SURFACES, ASYMPTOTIC SOLUTIONS | |||||||||
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| Issue or Number: | 6 | |||||||||
| DOI: | 10.1063/1.463917 | |||||||||
| Record Number: | CaltechAUTHORS:SIMjcp92 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:SIMjcp92 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 13231 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | Tony Diaz | |||||||||
| Deposited On: | 10 Jul 2009 21:32 | |||||||||
| Last Modified: | 08 Nov 2021 22:36 |
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