Journal of Chemical Physics, Vol.115, No.5, 2198-2206, 2001
Shifting and broadening in the fundamental band of CO highly diluted in He and Ar: A comparison with theory
We present measurements of the shifts and widths of the rovibrational lines of the fundamental band of CO highly diluted in He and Ar at 296 K. The shifts are decomposed into parts odd and even in the line number, m. These are then compared with close coupled calculations carried out with the best known interaction potentials. There is general agreement between the calculated and measured values of the broadening and shifting. Furthermore, the results illustrate that the decomposition of the shifts into parts, odd and even in m, is a powerful tool for separating out the relative contributions of the isotropic and anisotropic part of the interaction to the shifts and which part needs to be corrected if there is a discrepancy. Thus, shift measurements can be added to the list of experiments that may be used to determine reliable interaction potentials. The results also show, given a potential, that close coupled calculations are accurate and could be used to confirm or establish empirical models of the temperature dependence of the broadening or shifting, etc. Such modeling is important at atmospheric physics.