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Vibrational deactivation on chemically reactive potential surfaces: An exact quantum study of a low barrier collinear model of H + FH, D + FD, H + FD and D + FH

Schatz, George C. and Kuppermann, Aron (1980) Vibrational deactivation on chemically reactive potential surfaces: An exact quantum study of a low barrier collinear model of H + FH, D + FD, H + FD and D + FH. Journal of Chemical Physics, 72 (4). pp. 2737-2743. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:20120718-141228051

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Abstract

We study vibrational deactivation processes on chemically reactive potential energy surfaces by examining accurate quantum mechanical transition probabilities and rate constants for the collinear H + FH(v), D + FD(v), H + FD(v), and D + FH(v) reactions. A low barrier (1.7 kcal/mole) potential surface is used in these calculations, and we find that for all four reactions, the reactive inelastic rate constants are larger than the nonreactive ones for the same initial and final vibrational states. However, the ratios of these reactive and nonreactive rate constants depend strongly on the vibrational quantum number v and the isotopic composition of the reagents. Nonreactive and reactive transition probabilities for multiquantum jump transitions are generally comparable to those for single quantum transitions. This vibrationally nonadiabatic behavior is a direct consequence of the severe distortion of the diatomic that occurs in a collision on a low barrier reactive surface, and can make chemically reactive atoms like H or D more efficient deactivators of HF or DF than nonreactive collision partners. Many conclusions are in at least qualitative agreement with those of Wilkin’s three dimensional quasiclassical trajectory study on the same systems using a similar surface. We also present results for H + HF(v) collisions which show that for a higher barrier potential surface (33 rather than 1.7 kcal/mole), the deactivation process becomes similar in character to that for nonreactive partners, with v→v−1 processes dominating.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1063/1.439421DOIUNSPECIFIED
http://link.aip.org/link/doi/10.1063/1.439421PublisherUNSPECIFIED
Additional Information:© 1980 American Institute of Physics. Received 23 March 1979; accepted 12 June 1979. Research supported in part by the United States Air Force Office of Scientific Research. Work performed in partial fulfillment of the requirements for the Ph. D. in Chemistry at the California Institute of Technology.
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Funding AgencyGrant Number
Air Force Office of Scientific Research (AFOSR)UNSPECIFIED
Subject Keywords:Dissociation; photolysis; xenon fluorides; crystal lattices; xenon; krypton; synchrotron radiation; emission spectra; luminescence
Classification Code:PACS: 82.50.Hp; 33.80.Gj
Record Number:CaltechAUTHORS:20120718-141228051
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20120718-141228051
Official Citation:Vibrational deactivation on chemically reactive potential surfaces: An exact quantum study of a low barrier collinear model of H + FH, D + FD, H + FD and D + FH George C. Schatz and Aron Kuppermann, J. Chem. Phys. 72, 2737 (1980), DOI:10.1063/1.439421
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:32562
Collection:CaltechAUTHORS
Deposited By: Jason Perez
Deposited On:18 Jul 2012 21:48
Last Modified:26 Dec 2012 15:36

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