On the role of the imaginary part of the relaxation matrix in vibration-rotation bandshape calculations

Nikolai N. Filippov; Mikhail V. Tonkov

doi:10.1117/12.545652

12 January 2004 The role of the imaginary part of the relaxation matrix in vibration-rotation bandshape calculations

Nikolai N. Filippov, Mikhail V. Tonkov

Proceedings Volume 5311, 14th Symposium on High-Resolution Molecular Spectroscopy; (2004) https://doi.org/10.1117/12.545652
Event: 14th Symposium on High-Resolution Molecular Spectroscopy, 2003, Krasnoyarsk, Russian Federation

Abstract

To study the role of the off-diagonal imagery part of the relaxation matrix in the bandshape formation, the phase factor exp(-iα) has been introduced into empirical ECS expressions for the basic cross-section calculations. Analyzing the high-density 3v₃ CO₂ bandshapes in CO₂ - Ar gas mixtures, which are extremely sensitive to details of the line mixing effect, we have found that the off-diagonal imagery part of the matrix causes the sufficient shift of the band. Moreover, it causes decreasing the maximum of the branch R and increasing the maximum of the branch P. These effects correspond to the deviations between the measured and ECS calculated band profiles obtained in Ref. 1. This analysis leads to conclusion that the neglect of the off-diagonal imagery part of the relaxation matrix can provide systematic deviations of calculated spectral bandshape from observed one.

Citation Download Citation

Nikolai N. Filippov and Mikhail V. Tonkov "The role of the imaginary part of the relaxation matrix in vibration-rotation bandshape calculations", Proc. SPIE 5311, 14th Symposium on High-Resolution Molecular Spectroscopy, (12 January 2004); https://doi.org/10.1117/12.545652

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