Interbranch line-mixing in CO2 (1001) and (0201) combination bands
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Absorption spectra from a mixture of 320 ppm CO2 in synthetic air (79% N2, 21% O2) were collected in the region from 3500 cm-1 to 4000 cm-1 under conditions in the range of 100-1000 atm and 295-900 K. At 295 K, both bands of the (10 1), (02 1) Fermi dyad show the collapse of P and R branches into a single nearly Lorentzian spectral feature as a result of interbranch line-mixing. At elevated temperatures, the presence of interbranch mixing is also clearly evident as is the presence of several hot bands. The experimental data are modeled using two methods for simulating line-mixed spectra; first, the usual line-by-line approach which relies on the binary impact approximation, and second, a simple band-averaged model proposed by Hartmann and L'Haridon [J. Chem. Phys. 103, 6467 (1995)]. The energy corrected sudden (ECS) approximation is used to generate the relaxation matrix in the first approach. Comparison with the measurement shows that the ECS method does not fit the high density data satisfactorily when adjustable parameters from the literature are used; the level of interbranch mixing must be decreased by about a factor of 2 relative to intrabranch mixing and at least 5% dephasing must be added to the ECS matrix. With these changes, the room temperature data are modeled satisfactorily, but significant discrepancies are still present in the high temperature spectra. On the other hand, the simpler band-averaged model does provide a reasonable estimate of the spectra for all temperatures when best fit values are used for mixing and broadening, but the low density data are not reproduced as well as with the ECS model. Data from high pressure absorption measurements in a 1% NO in N2 mixture as well as a 0.5% CH4 in N2 mixture are also presented without analysis, showing the effects of interbranch line-mixing in these spectra. 1997 American Institute of Physics.
The Journal of Chemical Physics
author list (cited authors)
Gillespie, W. D., Meinrenken, C. J., Lempert, W. R., & Miles, R. B.