A simple approximate version of the Fock-space relativistic coupled-cluster method is developed and applied for modeling the spin-orbit-coupling effect in the A1Σ(u)+ and b3Π(u) states of the heavy alkali diatomics RbCs and Cs2. Numerical stability in a wide range of molecular geometries is achieved at the cost of a very moderate loss of accuracy for low-lying states and negligibly small deviations of the computational scheme from strict size consistency. The adiabatic potential energy curves computed for the (2,3)0+ (RbCs) and (1,2)0u+ (Cs2) states are converted into "quasidiabatic" potentials and effective spin-orbit-coupling functions via projection of the scalar relativistic states onto the subsets of fully relativistic states. A detailed comparison of the present ab initio results with their experimental and preceding theoretical counterparts is performed.
| Original language | English |
|---|---|
| Article number | 022516 |
| Journal | Physical Review A |
| Volume | 96 |
| Issue number | 2 |
| DOIs | |
| State | Published - 29 Aug 2017 |
| Externally published | Yes |
ID: 11879154