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ON THE GENERAL FEATURES IN COLLISION-INDUCED SPECTRA OF $N_{2}$, $O_{2}$, AND $CO_{2}$

Please use this identifier to cite or link to this item: http://hdl.handle.net/1811/20184

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Title: ON THE GENERAL FEATURES IN COLLISION-INDUCED SPECTRA OF $N_{2}$, $O_{2}$, AND $CO_{2}$
Creators: Vigasin, A. A.
Issue Date: 2001
Abstract: Collision-induced absorption (CIA) in gases is generally believed to arise as a result of elastic molecular pair collisions. In some cases true dimers are recognized to contribute to the observed CIA, though the decomposition of CIA profiles into true bound and unbound pair contributions bears substantial ambiguity until recently. Present paper aims at drawing attention to the general features in CIA spectra which may throw a new light on the nature of CIA phenomenon. The retrieval of these features is supported by theoretical consideration of CIA spectra of $N_{2}$, $O_{2}$ and $CO_{2}$ taken recently at high resolution using FTIR technique. First, the attention is drawn to the use of statistical physics partitioning to subdivide CIA intensity among true bound, quasibound and free pair contributions. It is demonstrated that in case of $CO_{2}$ the theory matches nicely the experimental observations as far as temperature variations of true dimers fraction are concerned. Second, the role played by linemixing effect in the formation of CIA profiles is discussed. Moderate line-mixing in case of $N_{2}$ and $O_{2}$ fundamentals results in appearance of the so-called ripples in the room-temperature CIA spectra. In $CO_{2}$ the line-mixing is likely to symmetrize the background profile. Third, the mechanisms responsible for the shaping of the true dimer absorption profiles in CIA spectra are discussed. Attention is paid to nonrigidity of dimers as well as to specific selection rules $\Delta J = 3D0$, $\pm 1$, $\pm 3$ appropriate to induced absorption. Rotational predissociation effect and $N$ and $T$ branches are shown to manifest themselves in the dimeric constituent of the $CO_{2}$ CIA spectra in the region of the Fermi doublet.
URI: http://hdl.handle.net/1811/20184
Other Identifiers: 2001-TA-07
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