Relativistic EOM-CCSD for Core-Excited and Core-Ionized State Energies Based on the Four-Component...

We report an implementation of the core-valence separation approach to the four-component relativistic Hamiltonian-based equation-of-motion coupled-cluster with singles and doubles theory (CVS-EOM-CCSD) for the calculation of relativistic core-ionization potentials and core-excitation energies. With this implementation, which is capable of exploiting double group symmetry, we investigate the effects of the different CVS-EOM-CCSD variants and the use of different Hamiltonians based on the exact two-component (X2C) framework on the energies of different core-ionized and -excited states in halogen- (CH₃I, HX, and X^-, X = Cl-At) and xenon-containing (Xe, XeF₂) species. Our results show that the X2C molecular mean-field approach [Sikkema, J.; J. Chem. Phys. 2009, 131, 124116], based on four-component Dirac-Coulomb mean-field calculations (²DC), is capable of providing core excitations and ionization energies that are nearly indistinguishable from the reference four-component energies for up to and including fifth-row elements. We observe that two-electron integrals over the small-component basis sets lead to non-negligible contributions to core binding energies for the K and L edges for atoms such as iodine or astatine and that the approach based on Dirac-Coulomb-Gaunt mean-field calculations (²DCG) are significantly more accurate than X2C calculations for which screened two-electron spin-orbit interactions are included via atomic mean-field integrals.