AB initio MRD CI potential curves, dipole moments and zero-field splittings for the X 2Π ground states of the CF and CCl molecules

Abstract

A series of ab initio MRD CI calculations at various levels of theoretical treatment is carried out for the X 2Π ground states of the CF and CCl molecules. The resulting potential energy curves lead to quite good agreement with known spectroscopic constants for these systems and also allow for the accurate computation of the corresponding vibrational wavefunctions. Particular attention is given to the dependence of the electric dipole moments and spin-orbit splittings on the choice of the one-electron basis in the CI calculations. Best agreement with experimental values for these quantities is obtained by employing the natural orbitals of X 2Π states, in which case errors of only 0.1–0.2 D and 2.0–4.0 cm −1 respectively in the computed dipole moments and zero-field splittings result.