ИСТИНА

We performed a first principle calculation of the adiabatic potential energy curves (PECs), permanent and transition dipole moments as well as spin-orbit and angular (Coriolis) coupling matrix elements among the LiRb states converging to the lowest four dissociation limits. Particular attention has been paid to their correct long-range behavior. The electronic structure was evaluated for a wide range of internuclear distances in the basis of the spin-averaged wavefunctions corresponding to the pure Hund's coupling case (a) by using small (including the 2/8 subvalence + 1 valence electrons) effective core pseudopotentials (ECP) for both atoms. An all electron basis set of quadrupole zeta valence quality was additionally used to the Li atom to elucidate the core-polarization effect. The dynamic correlation is accounted for in a large scale multi-reference configuration interaction (MR-CI) method applied to only two valence (or 2 core + 2 valence) electrons. The core-polarization potentials (CPP) were implemented in all cases to implicitly take the residual core-valence effect into account. The PECs convergence was monitored by saturation of the atomic basis above by the bound functions centered at the midpoint of the internuclear distance. The reliability of the present adiabatic potentials and dipole moment functions are accessed through comparison with their preceding theoretical and experimental counterparts [1]. The ab initio PECs, spin-orbit and angular coupling matrix elements were used in coupled-channel deperturbation analysis of the lowest (1,2)1Π states. The empirically refined PECs and non-adiabatic electronic matrix elements allowed us to represent overall set of the experimental rovibronic energies for both locally and regularly perturbed states within uncertainty of the Fourier-transform measurements, ~0.01 cm-1.