title: Ab initio ro-vibronic spectroscopy of SiCCl (X̃(2)Π).
abstract: The full dimensional potential energy surfaces of the (2)A' and (2)A'' electronic components of X̃(2)Π SiCCl have been computed using the explicitly correlated coupled cluster method, UCCSD(T)-F12b, combined with a composite approach taking into account basis set incompleteness, core-valence correlation, scalar relativity, and higher order excitations. The spin-orbit and dipole moment surfaces have also been computed ab initio. The ro-vibronic energy levels and absorption spectrum at 5 K have been determined from variational calculations. The influence of each correction on the fundamental frequencies is discussed. An assignment is proposed for bands observed in the LIF experiment of Smith et al. [J. Chem. Phys. 117, 6446 (2002)]. The overall agreement between the experimental and calculated ro-vibronic levels is better than 7 cm(-1) which is comparable with the 10-20 cm(-1) resolution of the emission spectrum.
authors: Université d'Evry Val d'Essonne, Laboratoire Analyse et Modélisation pour la Biologie et l'Environnement, LAMBE CNRS UMR 8587, Boulevard F. Mitterrand, 91025 Evry Cedex, France.
authors: Vincent
authors: V
authors: Brites
authors: Université Paris-Est, Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, 5 bd Descartes, 77454 Marne-la-Vallée, France.
authors: Alexander O
authors: AO
authors: Mitrushchenkov
authors: Department of Chemistry, Washington State University, Pullman, Washington 99164, USA.
authors: Kirk A
authors: KA
authors: Peterson
authors: Université Paris-Est, Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, 5 bd Descartes, 77454 Marne-la-Vallée, France.
authors: Céline
authors: C
authors: Léonard