Journal of the Chemical Society - Faraday Transactions p. 3205 - 3215 (1993)
Update date:2022-08-11
Topics:
Barnes, Martin P.
Carter, Robert T.
Lakin, Nicholas M.
Brown, John M.
Part of the electronic spectrum of copper dichloride, CuCl2, between 590 and 600 nm, has been recorded in the gas phase using a sample prepared at low temperatures (ca. 10 K) in a free jet expansion.Under these conditions it is possible to resolve vibrational, rotational and even hyperfine structure.Nine bands in this region have been analysed in detail.Six involve the dominant isotopomer, Cu(35)Cl2 and the other three the mixed form, Cu(35)Cl(37)Cl (it is not possible at this stage to identify the copper isotope).All the bands show parallel rotational structure of a linear molecule, consistent with an electronic assignment to a 2Πu-2Πg transition suggested by ab initio calculations.Seven of the bands are assigned as 2Π3/2-2Π3/2, one as 2Π1/2-2Π1/2 and the other as 2Δ5/2-2Δ5/2.The majority of the bands are thought to involve the molecule in its ground vibrational state but the last of these presumably involves excited vibrational levels in the bending vibration ν2.The Cu-Cl bond length determined from the lower-state rotational constant for Cu(35)Cl2 is r''0 = 0.203614(26) nm.The greater occurrence of transitions which involve the 2Π3/2 spin component suggests that this spin component is lower in energy than the 2Π1/2 component, contrary to theoretical expectations.The vibrational structure of the spectrum in the wavelength region studied is very complicated and no detailed vibrational assignments have been made.It is thought that the (0-0) band of the electronic transition lies at significantly longer wavelengths than those covered in this study.
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