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Measurement of room temperature absorption by PH3–H2 mixtures in the v2 and v4 bands of phosphine (PH3) have been made for low pressures. Fits of these spectra are made for the determination of the width for isolated lines, and line mixing in first-order Rosenkranz approximation. From the previous determinations, we deduce some remarks on the lack of accuracy for the prediction of the collisional process. With the first-order Rosenkranz approximation, the collisional parameters are considered linear with pressure. In this work, we have considered some spectra recorded for three doublets A1 and A2 lines in the v2 and v4 bands of PH3 diluted with higher H2 pressure. We show that the line shifts are non-linear with perturber pressures, which requires testing the fits of the recorded spectra by profiles developed in the second-order approximation of the perturbation theory. Consequently, the first and second-order mixing coefficients are determined and discussed. Also, through this study, we show that the change of the intensities distribution is provided by the populations exchange between the low energy levels for the two components of doublets A1 and A2 lines and is described through the second-order mixing parameter. Thereby, we show the mixing effect on the line width.

science journal of chemistry

Infrared Line Collisional Parameters of PH&amp;lt;sub&amp;gt;3&amp;lt;/sub&amp;gt; in Hydrogen: Measurements with Second-order Approximation of Perturbation Theory