Relativistic Two-component Double Ionization Potential Equation-of-Motion Coupled Cluster with the Dirac--Coulomb--Breit Hamiltonian

Abstract: We present an implementation of relativistic double-ionization-potential (DIP) equation-of-motion coupled-cluster (EOMCC) with up to 4-hole--2-particle ($4h2p$) excitations that makes use of the molecular mean-field exact two-component (mmfX2C) framework. We apply mmfX2C-DIP-EOMCC to several neutral atoms and diatomic molecules to obtain the ground and first few excited states of the corresponding di-cation species, and we observe excellent agreement (to within 0.001 eV) between double ionization potentials (IPs) obtained from mmfX2C- and four-component DIP-EOMCC calculations that include 3-hole--1-particle ($3h1p$) excitations, with either the Dirac--Coulomb or Dirac--Coulomb--Gaunt Hamiltonians. We also compare double IPs for mmfX2C-DIP-EOMCC calculations with the full Dirac--Coulomb--Breit (DCB) Hamiltonian to those from experiment. The mmfX2C-DIP-EOMCC with $3h1p$ excitations leads to errors in absolute double IPs that are larger than 0.1 eV, whereas the addition of $4h2p$ excitations reduces these errors dramatically, often by an order of magnitude or more.