Insight into the Rydberg states of CH

Vázquez, G. J.; Amero, J. M.; Liebermann, H. P.; Buenker, R. J.; Lefebvre-Brion, H.
April 2007
Journal of Chemical Physics;4/28/2007, Vol. 126 Issue 16, p164302
Academic Journal
Ab initio electronic structure calculations of a relatively large number of Rydberg states of the CH radical were carried out employing the multireference single and double excitation configuration interaction (MRD-CI) method. A Gaussian basis set of cc-pV5Z quality augmented with 12 diffuse functions was used together with an extensive treatment of electron correlation. The main focus of this contribution is to investigate the 3d Rydberg complex assigned by Watson [Astrophys. J. 555, 472 (2001)] to three unidentified interstellar bands. The authors’ calculations reproduce quite well the absolute excitation energies of the three components of the 3d complex, i.e., 2Σ+(3dσ), 2Π(3dπ), and 2Δ(3dδ), but not the energy ordering inferred from a rotational assignment of the 3d←X 2Π laboratory spectrum. The computation of the 4d complex is reported for the first time along with a number of other higher lying Rydberg species with an X 1Σ+ core. The lowest Rydberg states belonging to series converging to the a 3Π and A 1Π excited states of CH+ are also calculated.


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