Relativistic Ab Initio Treatment of the Second-Order Spin-Orbit Splitting of the α 3Σ+u Potential of Rubidium and Cesium Dimers
Svetlana A. Kotochigova, Eite Tiesinga, Paul S. Julienne
We have calculated the splitting between the 0 and 1u components of the a3S state of Rb2 and Cs2 using a relativistic ab initio configuration-interaction valence bond method. This so-called second-order spin-orbit splitting is entirely due to relativistic correlations within the molecule. A comparison between ab initio and perturbative calculations is given. Our nonperturbative splitting is five and two times larger at the inner turning point of the a3S potential for Rb2 and Cs2, respectively. In addition, close-coupled nuclear dynamics calculations that estimate the effect of this splitting on experimentally accessible quantities, are presented. The splitting affects the collisional loss rate of magnetically trapped ultra-cold Rb and Cs atoms and the spectroscopic determination of the vibrational structure of Rb2 and Cs2 dimers. Agreement with the experimental collisional loss rates of Cs is found.
Physical Review A (Atomic, Molecular and Optical Physics)
, Tiesinga, E.
and Julienne, P.
Relativistic Ab Initio Treatment of the Second-Order Spin-Orbit Splitting of the α <sup>3</sup>Σ<sup>+</sup><sub>u</sub> Potential of Rubidium and Cesium Dimers, Physical Review A (Atomic, Molecular and Optical Physics)
(Accessed February 25, 2024)