Coupled-cluster method for open-shell heavy-element systems with spin-orbit coupling.

Abstract

The coupled-cluster approach with spin-orbit coupling (SOC) included in post-self-consistent field treatment (SOC-CC) using relativistic effective core potentials is extended to spatially non-degenerate open-shell systems in this work. The unrestricted Hartree-Fock determinant corresponding to the scalar relativistic Hamiltonian is employed as the reference and the open-shell SOC-CC approach is implemented at the CC singles and doubles (CCSD) level as well as at the CCSD level augmented by a perturbative treatment of triple excitations (CCSD(T)). Due to the breaking of time-reversal symmetry and spatial symmetry, this open-shell SOC-CC approach is rather expensive compared with the closed-shell SOC-CC approach. The open-shell SOC-CC approach is applied to some open-shell atoms and diatomic molecules with s1, p3, σ1, or π2 configuration. Our results indicate that rather accurate results can be achieved with the open-shell SOC-CCSD(T) approach for these systems. Dissociation energies for some closed-shell molecules containing heavy IIIA or VIIA atoms are also calculated using the closed-shell SOC-CC approach, where energies of the IIIA or VIIA atoms are obtained from those of the closed-shell ions and experimental ionization potentials or electron affinities. SOC-CCSD(T) approach affords reliable dissociation energies for these molecules. Furthermore, scalar-relativistic CCSD(T) approach with the same strategy can also provide reasonable dissociation energies for the 5th row IIIA or VIIA molecules, while the error becomes pronounced for the 6th row elements.