Theoretical Study of the Rovibronic States of CaO

H. Khalil (1) , Frédéric Le Quéré (1) , V. Brites (1) , Céline Léonard (1)

1 MSME - Laboratoire de Modélisation et Simulation Multi Echelle

The spin-rovibronic energy levels of CaO, which result from the couplings of X(1)Sigma(+), a(3)Pi, A'(1)Pi, b(3)Sigma(+), and A(1)Sigma(+) low-lying electronic states, are determined from wave packet time propagations and Prony analysis. The electronic potentials were taken from our previous study [Chem. Phys., 386, 50 (2011)]. The spin-orbit and (L) over cap coupling functions were determined by CASSCF and MRCI calculations. The effects of spin-orbit coupling on vibrational levels were analyzed in the Omega=0(+), 0(-), 1 coupling schemes. All spin-vibronic energy levels associated with the a(3)Pi, A'(1)Pi, b(3)Sigma(+), and A(1)Sigma(+) states were determined up to 16000 cm(-1) above the electronic ground-state minimum. The results obtained from the spin-orbit coupling functions are in remarkable agreement with the experimental data extracted using a deperturbation procedure. The final energies calculated for J = 2 and J = 25 are used to compare the experimental observations concerning the X(1)Sigma(+)-A(1)Sigma(+) transition. (C) 2011 Elsevier Inc. All rights reserved.

H. Khalil, Frédéric Le Quéré, V. Brites, Céline Léonard. Theoretical Study of the Rovibronic States of CaO. Journal of Molecular Spectroscopy, 2012, 271 (1), pp.1-9. ⟨10.1016/j.jms.2011.10.004⟩. ⟨hal-00692707⟩