The relaxation matrix for symmetric tops with inversion symmetry. II. Line mixing effects in the ν1 band of NH3.
Line mixing effects have been calculated in the ν1 parallel band of self-broadened NH3. The theoretical approach is an extension of a semi-classical model to symmetric-top molecules with inversion symmetry developed in the companion paper [Q. Ma and C. Boulet, J. Chem. Phys. 144, 224303 (2016)]. This model takes into account line coupling effects and hence enables the calculation of the entire relaxation matrix. A detailed analysis of the various coupling mechanisms is carried out for Q and R inversion doublets. The model has been applied to the calculation of the shape of the Q branch and of some R manifolds for which an obvious signature of line mixing effects has been experimentally demonstrated. Comparisons with measurements show that the present formalism leads to an accurate prediction of the available experimental line shapes. Discrepancies between the experimental and theoretical sets of first order mixing parameters are discussed as well as some extensions of both theory and experiment.
Institut des Sciences Moléculaires d'Orsay (ISMO), CNRS, Univ. Paris-Sud, Université Paris-Saclay, Bât. 350, Campus d'Orsay F-91405, France.
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NASA/Goddard Institute for Space Studies and Department of Applied Physics and Applied Mathematics, Columbia University, 2880 Broadway, New York, New York 10025, USA.
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