Xenon-broadened CO line shapes in the fundamental band at 349 KThis article is part of a Special Issue on Spectroscopy at the University of New Brunswick in honour of Colan Linton and Ron Lees.

Abstract

We present a line shape analysis of the P(2) and P(7) transitions of CO broadened by Xe in the fundamental band. The spectra were recorded at 349 K using a difference frequency laser spectrometer. To obtain information on the influence of Dicke narrowing, relaxation speed dependence, and line mixing effects, several models for implementation of Dicke narrowing and (or) speed-dependent effects are discussed. From experimental data analysis, we conclude that line shape models taking into account the Dicke effect only fail in the high pressure regime and lead to optical diffusion parameters that are much larger than the kinetic diffusion ones. On the contrary, a fair interpretation of data is obtained from speed-dependent models, so that it is possible to derive a quantitative estimate of optical diffusion effects that appear much smaller than the kinetic diffusion ones. Xe-broadening coefficients of CO lines in the fundamental band at 297 and 349 K are calculated from a semiclassical formalism involving successively two intermolecular potentials, the atom-atom Lennard-Jones model, and a three-term expansion of Legendre polynomials with four adjustable parameters.