Approximate relativistic coupled-cluster calculations on heavy alkali-metal diatomics: Application to the spin-orbit-coupled A1 Σ+ and b3 Π states of RbCs and Cs2

A. Zaitsevskii, N. S. Mosyagin, A. V. Stolyarov, E. Eliav

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Abstract

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 languageEnglish
Article number022516
JournalPhysical Review A
Volume96
Issue number2
DOIs
StatePublished - 29 Aug 2017

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