ON THE ORIGIN OF THE BAND STRUCTURE OBSERVED IN THE COLLISION-INDUCED ABSORPTION BANDS OF $CO_{2}$

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Title: ON THE ORIGIN OF THE BAND STRUCTURE OBSERVED IN THE COLLISION-INDUCED ABSORPTION BANDS OF $CO_{2}$
Creators: Baranov, Y. I.; Lafferty, W. J.; Fraser, G. T.; Vigasin, A. A.
Issue Date: 2003
Publisher: Ohio State University
Abstract: Two collision-induced (CIA) IR bands of $CO_{2}$ are observed in the region of the Raman allowed $\nu_{1}- 2\nu_{2}$ Fermi-dyad monomer bands in the $7 \mu$ m region. These bands consist of a featureless CIA component upon which are superimposed very distinctive $CO_{2}$ dimer bands. The original observation of band structure in these bands was made by Welsh $et al.^{a}$ and was interpreted by $Mannik et al.^{b}$ to be the P-, Q- and R-branches of a T-shaped dimer. However, molecular beam $studies^{c}$ have subsequently shown that the dimer bands consist of nearly equally intense a-type and b-type transitions and that the dimer structure is a slipped-parallel arrangement with $C_{2h}$ symmetry. Recently Vigasin and $Baranov^{d}$ have modeled the dimer profile observed in room temperature CIA spectra using a symmetric-rotor model which leads to a derived C-C separation of $4.46 \AA$ considerably larger than the molecular beam value of $3.3986 \AA$. In this report, we suggest an alternative explanation for the dimer band profile observed. We have modeled the bands using a Watson asymmetric-rotor Hamiltonian and the rotational constants derived in a molecular beam study. We have varied only the upper-state A rotational constant and the $\mu_{a}/\mu_{b}$ ratio. In this model, the band structure is not due to P- Q, and R-branches but rather to a central sharp a-type Q-branch with broad b-type Q-branches on either side of the band center. All the Q-branch transitions sit on a pedestal of unresolved $^{p}P-$ and $^{r}R$-branch lines. Comparison with observed spectra is good but not perfect and departures from the model will be discussed.
Description: $^{a}$H.L. Welsh, M.F. Crawford and J.L. Locke, Phys. Rev, 76, 580 (1949) $^{b}$L. Mannik, J.C. Stryland and H.L Welsh, Can. J. Phys. 49, 3056 (1971). $^{c}$K.W. Jucks et al., J. Chem. Phys., 88, 2185(1988); M.A. Walsh et al., Chem. Phys. Lett. 142, 265 (1987). $^{d}$Y.I. Baranov and A.A. Vigasin, J. Mol. Spectrosc. 193, 319 (1999); A.A. Vigasin, J. Mol. Spectrosc. 200, 89 (2000).
Author Institution: Optical Technology Division, NIST, Gaithersburg; General Physics Institute, Russian Academy of Sciences
URI: http://hdl.handle.net/1811/20747
Other Identifiers: 2003-FB-06
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