Collisional energy transfer at high temperatures from the biased walk model

Gilbert, R.G. and Oref, I. (1991) Collisional energy transfer at high temperatures from the biased walk model. Journal of Physical Chemistry, 95 13: 5007-5011. doi:10.1021/j100166a021


Author Gilbert, R.G.
Oref, I.
Title Collisional energy transfer at high temperatures from the biased walk model
Journal name Journal of Physical Chemistry   Check publisher's open access policy
ISSN 0022-3654
1541-5740
Publication date 1991-06
Sub-type Article (original research)
DOI 10.1021/j100166a021
Volume 95
Issue 13
Start page 5007
End page 5011
Total pages 5
Place of publication Washington, DC, United States
Publisher American Chemical Society
Language eng
Formatted abstract
A new expression for the probability, P(E,E′), of collisional energy transfer for large polyatomics at high temperatures is deduced by using the assumptions of the biased random walk (BRW) model [Lim, K. F.; Gilbert, R. G. J. Chem. Phys. 1986, 84, 6124] and of a Gaussian equilibrium population distribution. The latter approximation is shown to be very accurate at sufficiently high temperatures. Simple analytic expressions are obtained for P(E,E′), which show the correct limiting weak- and strong-collision forms as the duration of a collision approaches zero and infinity, respectively. Expressions are found for the average energy-transfer quantities 〈ΔEall〉, 〈ΔEd〉, and 〈ΔE2〉, as functions of initial energy E′. The expression for 〈ΔEall〉 explicitly shows the change of sign as E′ is varied over a wide range of E′. The new BRW expression for P(E,E′) can be accurately approximated as Gaussian. The derived expressions will be of use in modeling high-temperature processes such as combustion.
Keyword Thermal unimolecular reactions
Vibrationally excited molecules
Transfer quantities
Azulene
Deactivation
Activation
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Non-UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: School of Chemistry and Molecular Biosciences
Centre for Nutrition and Food Sciences Publications
 
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Created: Mon, 07 Mar 2011, 15:45:49 EST