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Relaxation Matrix for Symmetric Tops with Inversion Symmetry: Line Coupling and Line Mixing Effects on NH3 Lines in the nu4 Band

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

Line shape parameters including the half-widths and the off-diagonal elements of the relaxation matrix have been calculated for self-broadened NH3 lines in the perpendicular nu4 band. As in the pure rotational and the parallel nu1 bands, the small inversion splitting in this band causes a complete failure of the isolated line approximation. As a result, one has to use formalisms not relying on this approximation. However, due to differences between parallel and perpendicular bands of NH3, the applicability of the formalism used in our previous studies of the nu1 band and other parallel bands must be carefully verified. We have found that, as long as potential models only contain components with K1 = K2 = 0, whose matrix elements require the selection rule ∆k = 0, the formalism is applicable for the nu4 band with some minor adjustments. Based on both theoretical considerations and results from numerical calculations, the non-diagonality of the relaxation matrices in all the PP, RP, PQ, RQ, PR, and RR branches is discussed. Theoretically calculated self-broadened half-widths are compared with measurements and the values listed in HITRAN 2012. With respect to line coupling effects, we have compared our calculated intra-doublet off-diagonal elements of the relaxation matrix with reliable measurements carried out in the PP branch where the spectral environment is favorable. The agreement is rather good since our results do well reproduce the observed k and j dependences of these elements, thus validating our formalism.

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Title
The Journal of Chemical Physics
DOI
https://doi.org/10.1063/1.4979492

More About This Work

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