Interatomic potentials, electric properties, and spectroscopy of the ground and excited states of the Rb₂ molecule: Ab initio calculations and effect of a non-resonant field

الأصل · EN

We formulate the theory for a diatomic molecule in a spatially degenerate electronic state interacting with a non-resonant laser field and investigate its rovibrational structure in the presence of the field. We report on ab initio calculations employing the double electron attachment intermediate Hamiltonian Fock space coupled cluster method restricted to single and double excitations for all electronic states of the Rb₂ molecule up to 5s+5d dissociation limit of about 26.000cm⁻¹. In order to correctly predict the spectroscopic behavior of Rb₂, we have also calculated the electric transition dipole moments, non-adiabatic coupling and spin-orbit coupling matrix elements, and static dipole polarizabilities, using the multireference configuration interaction method. When a molecule is exposed to strong non-resonant light, its rovibrational levels get hybridized. We study the spectroscopic signatures of this effect for transitions between the X¹Σg+ electronic ground state and the A¹Σᵤ+ and b³Πᵤ excited state manifold. The latter is characterized by strong perturbations due to the spin-orbit interaction. We find that for non-resonant field strengths of the order 10⁹W/cm², the spin-orbit interaction and coupling to the non-resonant field become comparable. The non-resonant field can then be used to control the singlet-triplet character of a rovibrational level.