A comparison between the one- and two-step spin-orbit coupling approaches based on the ab initio density matrix renormalization group.

Abstract

The efficient and reliable treatment of both spin-orbit coupling (SOC) and electron correlation is essential for understanding f-element chemistry. We analyze two approaches to the problem: the one-step approach, where both effects are treated simultaneously, and the two-step state interaction approach. We report an implementation of the ab initio density matrix renormalization group with a one-step treatment of the SOC effect, which can be compared to prior two-step treatments on an equal footing. Using a dysprosium octahedral complex and bridged dimer as benchmark systems, we identify characteristics of problems where the one-step approach is beneficial for obtaining the low-energy spectrum.