Hydrogen line broadening in the ν2 and ν4 bands of phosphine at low temperature

Abstract

Using a tunable diode-laser spectrometer, we have measured H 2-broadening coefficients of PH 3 at low temperature (173.2 K) for 27 lines in the Q R branch of the ν 2 band and in the P P and R P branches of the ν 4 band. The recorded lines with J values ranging from 2 to 11 and K from 0 to 9 are located between 1016 and 1093 cm −1. The collisional widths are determined by fitting each spectral line with a Voigt profile and a speed-dependent Rautian profile which provides slightly larger broadening coefficients than the Voigt model. These coefficients have also been calculated on the basis of a semiclassical model of interacting linear molecules by considering an atom–atom Lennard–Jones potential in addition to the weak electrostatic contributions. Except for three Q R( J, K) lines, where K = J, the calculated broadening coefficients are in good agreement with the experimental data. By comparing the results obtained at room and low temperatures, the temperature dependence of linewidths has been determined both theoretically and experimentally.