Splittings of d⁸ configurations of late-transition metals with EOM-DIP-CCSD and FSCCSD methods

Multireference methods are usually required for transition metal systems due to the partially filled d electrons. In this work, the single-reference equation-of-motion coupled-cluster method at the singles and doubles level for double ionization potentials (EOM-DIP-CCSD) is employed to calculate energies of states from the d⁸ configuration of late-transition metal atoms starting from a closed-shell reference. Its results are compared with those from the multireference Fock-space coupled-cluster method at the CCSD level (FSCCSD) for DIP from the same closed-shell reference. Both scalar-relativistic effects and spin-orbit coupling are considered in these calculations. Compared with all-electron FSCCSD results with four-component Dirac-Coulomb Hamiltonian, FSCCSD with relativistic effective core potentials can provide reasonable results, except for atoms with unstable reference. Excitation energies for states in the (n - 1)d⁸ns² configuration are overestimated pronouncedly with these two methods, and this overestimation is more severe than those in the (n - 1)d⁹ns¹ configuration. Error of EOM-CCSD on these excitation energies is generally larger than that of FSCCSD. On the other hand, relative energies of most of the states in the d⁸ configuration with respect to the lowest state in the same configuration are predicted reliably with EOM-DIP-CCSD, except for the ³P₀ state of Hg²⁺ and states in Ir⁺. FSCCSD can provide reasonable relative energies for the several lowest states, while its error tends to be larger for higher states.