Study of the X²Π State of the SiCN/SiNC Renner-Teller System

V. Brites (1, 2) , Alexander Mitrushchenkov (1) , Céline Léonard (1)

1 MSME - Laboratoire de Modélisation et Simulation Multi Echelle
2 LAMBE - Laboratoire Analyse et Modélisation pour la Biologie et l'Environnement

The potential energy surfaces of both components of the X²Π electronic ground state of the double Renner-Teller SiCN/SiNC system are calculated at RCCSD(T)-F12 level of theory. The SiNC minimum is found to lie at 628 cm^-1 above the SiCN one. The isomerization transition state is found at 7583 cm^-1 on the ²A' surface and at 7936 cm^-1 on the ²A'' surface. The cyclic local minimum on surface ²A' is also reproduced by our potential energy surface and is located at 3901 cm^-1. The calculated potentials are used to simulate ro-vibrational spectroscopy employing the recently developed EVEREST variational code. It is shown that Renner-Teller interaction (ε =0.3043 for SiCN and ε =0.3874 for SiNC) and spin-orbit coupling are both very important for a correct description of the spectroscopy of this system. Comparison with available experimental measurement is reported.

Domaines: Chimie théorique et/ou physique

V. Brites, Alexander Mitrushchenkov, Céline Léonard. Study of the X²Π State of the SiCN/SiNC Renner-Teller System. Journal of Chemical Physics, 2013, 138 (10), pp.104311. ⟨10.1063/1.4794050⟩. ⟨hal-00790174⟩