Vibrational energy transfer in Ar–O₃ collisions: comparison of rotational sudden, breathing sphere, and classical calculations

Abstract

The state-specific vibrational energy transfer, ΔE _n , in collisions of excited ozone molecules with argon atoms is investigated by means of the quantum mechanical infinite order sudden approximation. Calculations are performed for the isotopomers ¹⁶O¹⁶O¹⁶O, ¹⁶O¹⁸O¹⁶O, and ¹⁶O¹⁶O¹⁸O. The infinite order sudden approximation yields an energy transfer which at low ozone energies exceeds the energy transfer previously obtained with the breathing sphere approximation by an order of magnitude. For energies close to the dissociation threshold, however, the mismatch is reduced to less than a factor of two. On the other hand, the rotational sudden energy transfer agrees well with the results of classical trajectory calculations over a wide range of ozone energies.

Keywords:

• ozone
• stabilisation
• energy transfer

Acknowledgements

Financial support by the Deutsche Forschungsgemeinschaft is gratefully acknowledged. The authors are grateful to S. Yu. Grebenshchikov for invaluable discussions and contributions. Especially the analysis of the energy transfer in terms of the polyad structure of the ozone spectrum in Section 3.1 and the related Figures 4 and 5 are his work. To the regret of the authors he could not be persuaded to co-author this article.

Notes

Note

1. Unfortunately, the correct volume elements have been neglected by mistake in the integrals in Equations (9) and (12) in 9. In the actual calculations, however, they have been taken into account.