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Demeio, L., S. Green, and L. Monchick, 1995: Effects of velocity changing collisions on line shapes of HF in Ar. J. Chem. Phys., 102, 9160-9166, doi:10.1063/1.468864.
The Generalized Hess Method (GHM) gives a line shape expression which is formally equivalent to the Rautian-Sobel'man hard collision model of Dicke narrowing, but differs radically in the definition of one of the relaxation terms. The relaxation term leading to pressure broadening is the same, but the term leading to Dicke narrowing and ultimately to Doppler line shapes at zero density differs in certain important respects: (1) in GHM it is a weighted sum of the pressure broadening coefficient and an optical diffusion coefficient and (2) there is no sharp distinction between "velocity changing" and "phase changing" collisions. The Dicke narrowing term should thus be understood as including both collision types irretrevably intermixed, with GHM providing a prescription for both relaxation terms. Applied to HF v=0→1, j→j±1 absorption spectra in a bath of Ar and using an accurate interaction potential obtained from spectra of the van der Waals complex and essentially exact close coupling scattering S-matrices, GHM provides a rather good description of recently measured line shapes.
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