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Molecular Physics
An International Journal at the Interface Between Chemistry and Physics
Volume 85, 1995 - Issue 5
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Original Articles

Vibronic structure of the CO2+ ion: reinvestigation of the antisymmetric stretch vibration in the [Xtilde], Ã, and [Btilde] states

Mark A. Johnson Department of Chemistry, Yale University, 225 Prospect Street, New Haven, CT, USA
&
Joëlle Rostas Laboratoire de Photophysique Moléculaire du CNRS and Institut de Physico-Chimie Moléculaire de l'Université de Paris-Sud, Bˆatiment 213, Université de Paris-Sud, 91405, Orsay Cedex, France
Pages 839-868 | Received 16 Aug 1994, Accepted 25 Sep 1994, Published online: 12 Aug 2008
 
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Abstract

We review the literature regarding v 3 excitation in the CO2 + ion and present a consistent scheme of vibronic assignments involving v 3 and 2v 3 in the Ã2Πu-[Xtilde]2Πg and [Btilde]2Σu +-[Xtilde]2Πg bands. A key new piece of information enabling this reanalysis is provided by LIF detection of several Ã(ν102)2Πu-[Xtilde](000)2Πg absorption bands which are not observed in emission spectroscopy. We combine this information with previous measurements of the Ã(ν101)2Πg-[Xtilde](001)2Πu bands and infrared work on the [Xtilde](001)2Πu-[Xtilde](000)2Πg transition to determine the Ã(ν10ν3)2Π level structure. We also carry out a rotational analysis of the Ã(202)2Πu-[Xtilde](000)2Πg band and identify a number of previously misassigned bands as arising from Ã(ν100)2Πu-[Xtilde](ν102)2Πg transitions. Precise molecular constants for the [Xtilde](002)2Πg level are obtained from a recent Ã(000)2Πu-[Xtilde](002)2Πg emission spectrum recorded using a Fourier transform spectrometer. Finally, identification of the [Btilde](001)2Σg +-[Xtilde](001)2Πu and [Btilde](002)2Σu +-[Xtilde](002)2Πg bands in the 12CO2 + and 13CO2 + emission spectra allows accurate determination of the antisymmetric stretch frequency of the [Btilde] state. The v 3 valucs for à and [Btilde] states thus obtained are 2685·3 cm-1 and 1847 cm-1, respectively.

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