Pressure broadening and shifting parameters for the spectral lines in the fundamental vibration–rotation bands of HBr and HI in mixtures with rare gases

Abstract We present experimental data on the previously unknown line broadening and shifting coefficients in the (2 ← 0) overtone vibration–rotation bands of the HBr and HI molecules in mixtures with several rare gases. The vibrational dependence of the isotropic and anisotropic components of the binary interaction potential is probed by separating the measured line shifts into parts symmetric and asymmetric in the line number m and by comparing with the previously published similar data for the fundamental bands of the same molecules. It is shown that the line shifts are dominated by the vibrational dependence of the isotropic potential. A linear correlation is found between the asymptotic values of the symmetric shifts in the overtone bands for all HX–Rg (X = F, Cl, Br, I) pairs and the respective C 6 long-range potential energy constants. Line broadening parameters in the overtone band of pure HBr are also reported.