Line mixing in parallel and perpendicular bands of CO2: A further test of the refined Robert-Bonamy formalism

Boulet, C.; Ma, Qiancheng; Tipping, R. H.

Starting from the refined Robert-Bonamy formalism [Q. Ma, C. Boulet, and R. H. Tipping, J. Chem. Phys. 139, 034305 (2013)], we propose here an extension of line mixing studies to infrared absorptions of linear polyatomic molecules having stretching and bending modes. The present formalism does not neglect the internal degrees of freedom of the perturbing molecules, contrary to the energy corrected sudden (ECS) modelling, and enables one to calculate the whole relaxation matrix starting from the potential energy surface. Meanwhile, similar to the ECS modelling, the present formalism properly accounts for roles played by all the internal angular momenta in the coupling process, including the vibrational angular momentum. The formalism has been applied to the important case of CO2 broadened by N2. Applications to two kinds of vibrational bands (Σ → Σ and Σ → Π) have shown that the present results are in good agreement with both experimental data and results derived from the ECS model.


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The Journal of Chemical Physics

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Academic Units
Applied Physics and Applied Mathematics
Published Here
June 1, 2017