H2-broadening coefficients in the ν2 and ν4 bands of PH3

Journal of Quantitative Spectroscopy and Radiative Transfer(2004)

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H2-broadening coefficients are measured for 41 transitions of PH3 in the QR branch of the ν2 band and the PP, RP, and PQ branches of the ν4 band, using a tunable diode-laser spectrometer. The recorded lines with J values ranging from 2 to 16 and K from 0 to 11 are located between 995 and 1106cm−1. The collisional widths are determined by fitting each spectral line with a Voigt profile, a Rautian profile, and a speed-dependent Rautian profile. The latter model provides larger broadening coefficients than the Voigt model. These coefficients γ0(J,K) are found to decrease slightly on the whole as J increases and they decrease significantly for K values approaching or equal to J(J⩾4). The H2-broadenings are also calculated on the basis of a semiclassical model of interacting linear molecules, using an atom–atom Lennard-Jones potential in addition to the weak electrostatic contributions. The theoretical results are in satisfactory agreement with the experimental data and reproduce the J and K dependencies of the broadenings, but the decrease observed for the QR(J,K) transitions with K=J is notably overestimated.
Phosphine,Hydrogen,Broadening coefficients,Tunable diode laser
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