2020 Articles

Line shape parameters of PH₃ transitions: Theoretical studies of self-broadened widths and line mixing effects

Boulet, Christian; Ma, Qiancheng

Line mixing effects have been calculated in various parallel and perpendicular bands of self-broadened PH₃ lines and compared with recent experimental data. The theoretical approach is an extension to symmetric tops with high inversion barrier of the formalism previously developed for NH₃ (Q. Ma and C. Boulet J. Chem. Phys. 144, 224303 (2016)). The model takes into account the non diagonality of the scattering operator within the linespace as well as, in a correct way, the double degeneracy of the j, k levels when k ≠ 0. Transitions between such levels should be considered as doublets whose components may be coupled by the line mixing process. It has been shown that, at low pressure, the inversion of the experimental data will strongly depend on the splitting between the two components of a doublet. When it is significant, one can measure independently both the width of one component and the intra-doublet coupling matrix element. Otherwise, one can only measure the sum of these two elements. Comparisons with measurements show that the present formalism leads to accurate predictions of the experimental line shapes.