State Interaction for Relativistic Four-Component Methods: Choose the Right Zeroth-Order Hamiltonian for Late-Row Elements

We present several schemes based on the spin-separation of the Dirac–Coulomb–Breit Hamiltonian for the perturbative treatment of relativistic four-component Hamiltonians within the state interaction framework. While state interaction approaches traditionally use zeroth-order scalar-relativistic states, we develop augmented zeroth-order Hamiltonians with increasing accuracy and investigate convergence to the variational limit as a function of the choice of zeroth-order Hamiltonian. The state interaction schemes developed in this work are benchmarked using ground-state fine-structure splitting of late-row atoms and diatomic hyrides. Although the scalar-relativistic zeroth-order Hamiltonian exhibits significant errors in ground-state fine-structure splitting, the predictive accuracy can be improved by augmenting the zeroth-order Hamiltonian with one- and two-electron vector-relativistic operators (e.g., spin–orbit, spin–spin, orbit–orbit). This work lays the theoretical foundation for the development of low-scaling, high-accuracy perturbative relativistic methods suitable for late-row elements.