Line shape asymmetries in Ar-broadened HF(v=1–0) in the Dicke-narrowing regime

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Abstract
Collisional line shapes have been measured for the fundamental band transitions of HF in an Ar buffer gas at T=296 K using a tunable difference‐frequency laser spectrometer. The broadening and shift coefficients are in excellent agreement with recent close‐coupling scattering cross section calculations [Green and Hutson, J. Chem. Phys. 100, 891 (1994)] based on a realistic intermolecular potential surface determined by high‐resolution infrared and microwave spectroscopy of the Ar–HF van der Waals complex. Below atmospheric pressure, the line shapes exhibit strong collisional (Dicke) narrowing of the Doppler distribution and a slight asymmetry which we model with hard collision (Rautian) or soft collision (Galatry) profiles modified for partial correlation between velocity‐ and state‐changing collisions.

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