Comparison of rotational relaxation rate laws to characterize the Raman Q-branch spectrum of CO at 295 K

We test the ability of the energy corrected sudden (ECS), modified exponential gap (MEG) and the statistical power-exponential gap (SPEG) rate laws to characterize line broadening and line interference in the CO Q-branch at 295 K. All three rate laws fit the experimental linewidth data. The ECS law...

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Bibliographic Details
Published in:Chemical physics letters 1989-09, Vol.161 (3), p.232-238
Main Authors: Looney, J.P., Rosasco, G.J., Rahn, L.A., Hurst, W.S., Hahn, J.W.
Format: Article
Language:English
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Summary:We test the ability of the energy corrected sudden (ECS), modified exponential gap (MEG) and the statistical power-exponential gap (SPEG) rate laws to characterize line broadening and line interference in the CO Q-branch at 295 K. All three rate laws fit the experimental linewidth data. The ECS law is found to predict too much spectral collapse. The MEG and SPEG laws both adequately model spectral collapse, but with different implications about the role of dipolar and quadrupolar symmetry forces in CO:CO line broadening. From semiclassical calculations of CO linewidths, we conclude that the SPEG law with a restriction to even Δ J changes is the more physically correct model.
ISSN:0009-2614
1873-4448
DOI:10.1016/S0009-2614(89)87066-6