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

Using a tunable diode-laser spectrometer, we have measured H2-broadening coefficients of PH3 at low temperature (173.2 K) for 27 lines in the QR branch of the ν2 band and in the PP and RP branches of the ν4 band. The recorded lines with J values ranging from 2 to 11 and K from 0 to 9 are located between 1016 and 1093cm−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 QR(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.