ИСТИНА

The rigorous deperturbation analysis is required for an accurate representation of fully mixed electronic states. For heavy alkali atom containing molecules the spin-orbit coupling becomes very important among other non-adiabatic interactions. The coupled-channel (CC) deperturbation analysis became the well-established procedure for solving the rovibronic problem with experimental accuracy. However, the implementation of the CC approach is based on the explicit knowledge of the non-adiabatic electronic matrix elements as function of r. The high level ab initio electronic structure calculation is apparently the best way of generating the needed matrix elements. We report the spin-orbit, angular and radial coupling matrix elements required for global deperturbation treatment of strongly coupled electronic states? converging to the lowest three dissociation limits of KRb molecule. The non-adiabatic matrix elemnts were obtained in a wide range of internuclear distances by means of both shape and energy consistent small (9 electrons) effective core pseudopotentials (ECPs).The dynamic correlation has been accounted for a large scale multi-reference configuration interaction method which was applied for only two valence electrons (other were frozen).The angular independent core polarization potentials (CPPs) were employed together with small core ECPs to take implicitly into account for the residual core-valence effect. The relevant adiabatic potential energy curves and electric dipole transition moments were evaluated as well. All electronic structure calculations were performed in a pure (a) Hund's case coupling scheme by means of the MOLPRO program package.