A simple model for product rovibrational distributions in elementary chemical reactions

Truhins, Kaspars, Marsh, Richard, McCaffery, Anthony and Whitely, Thomas W J (2000) A simple model for product rovibrational distributions in elementary chemical reactions. The Journal of Chemical Physics, 112:12. 5281 - 5291. ISSN 1089-7690

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Abstract

We explore the application of a simple model of collisional processes, developed initially for
inelastic collisions, to the analysis of product rovibrational states in elementary chemical reactions.
The model depicts collisional transfer as a process of momentum exchange ~predominantly
linear-to-angular momentum! and is modified to take account of change in center-of-mass and
enthalpy change that accompany reaction. The kinematics of center-of-mass shift derived by Elsum
and Gordon @J. Chem. Phys. 76, 3009 ~1982!# lead to two limiting cases based on the parameter b.
The kinematic extremes alternatively may be specified in terms of the molecular torque arm about
which interconversion of linear and angular momentum is effected. This torque arm length
approximates to the product bond length when b.0 and the reactant bond length when b.90°.
Our approach shares elements in common with the classical kinematic model of Elsum and Gordon
but is somewhat simpler and more transparent. The method is shown to give accurate peak values
of v, j states of the products of a wide range of elementary reactions for which experimental data
is available. Monte Carlo trajectory calculations based on the physical principles described here give
excellent fits to experimental v, j distributions in F+I2-->IF+I, H+D2-->HD+D, and
Cl+H2-->HCl+H using input data consisting of atomic radii, atomic masses, velocities, and reaction
enthalpies.

Item Type: Article
Schools and Departments: School of Life Sciences > Chemistry
Depositing User: Anthony McCaffery
Date Deposited: 06 Feb 2012 19:41
Last Modified: 06 Jun 2013 13:32
URI: http://sro.sussex.ac.uk/id/eprint/21789
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