Quasi-relativistic treatment of the low-lying KCs states

Abstract

The potential energy curves, permanent and transition dipole moments as well as spin-orbit and angular coupling matrix elements between the KCs electronic states converging to the lowest three dissociation limits were evaluated in the basis of the spin-averaged wavefunctions corresponding to pure Hund's coupling case (a). The quasi-relativistic matrix elements have been obtained for a wide range of internuclear distance by using of small (9-electrons) effective core pseudopotentials of both atoms. The core-valence correlation has been accounted for a large scale multi-reference configuration interaction method combined with semi-empirical core polarization potentials. The static dipole polarizabilities of the ground X-1 Sigma(+) and a(3)Sigma(+) states were extracted from the closed-shell coupled-cluster energies by the finite-field method. Among the singlet and triplet Sigma(+) states manifold the pronounced avoided crossing effect between repulsive walls of the (2,3)(3)Sigma(+) states has been discovered and analyzed by finite-difference calculation of radial coupling matrix elements. The resulting transition dipole moments and potentials were used to predict radiative lifetimes and emission branching ratios of excited vibronic states while the calculated angular coupling matrix elements were transformed to A-doubling constants of the (1,2)(1)Pi states and magnetic g-factor of the ground state. The accuracies of the present results are discussed by comparing with experimental data and preceding calculations. (C) 2009 Elsevier Inc. All rights reserved.