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# Modelling collisional energy transfer in highly excited molecules

Version 2 2024-06-03, 09:50

Version 1 2015-08-21, 11:50

journal contribution

posted on 2024-06-03, 09:50 authored by Kieran LimKieran Lim, RG GilbertData from classical trajectory simulations of the collision of a highly excited molecule with a monatomic bath gas are used to test the validity of the precepts used in the biased-random-walk (BRW) model for collisional energy transfer. This model assumes that energy migration during the collision is pseudorandom except for the constraint of microscopic reversibility, and leads to a simple displaced Gaussian form for the energy-transfer probability distribution. The BRW assumptions are shown to be of acceptable validity to exact classical trajectory simulations. A simple analytical approximation to the mean-square energy transfer per collision is obtained which reproduces the trajectory data to within an average of ±20%, and also gives acceptable accord with experimental data. The model shows that the magnitude of the average energy transferred per collision is governed by the time taken to traverse the overall interaction potential in and out from the appropriate collision diameter, by the internal energy, and by the average force exerted at the classical turning point of individual reactant-atom–bath-gas interactions.

## History

## Journal

Journal of Chemical Physics## Volume

92## Pagination

1819-1830## Publisher DOI

## ISSN

0021-9606## Notes

Data from classical trajectory simulations of the collision of a highly excited molecule with a monatomic bath gas are used to test the validity of the precepts used in the biased-random-walk (BRW) model for collisional energy transfer. This model assumes that energy migration during the collision is pseudorandom except for the constraint of microscopic reversibility, and leads to a simple displaced Gaussian form for the energy-transfer probability distribution. The BRW assumptions are shown to be of acceptable validity to exact classical trajectory simulations. A simple analytical approximation to the mean-square energy transfer per collision is obtained which reproduces the trajectory data to within an average of ±20%, and also gives acceptable accord with experimental data. The model shows that the magnitude of the average energy transferred per collision is governed by the time taken to traverse the overall interaction potential in and out from the appropriate collision diameter, by the internal energy, and by the average force exerted at the classical turning point of individual reactant-atom–bath-gas interactions.## Publication classification

CN.1 Other journal article## Copyright notice

1990, AIP Publishing## Issue

3## Publisher

AIP Publishing## Usage metrics

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