Efficient Spin-Orbit Coupling in Algebraic Diagrammatic Construction Theory: A State-Interaction Approach

Abstract

Spin-orbit coupling and electron correlation play important roles in a broad range of chemical and physical phenomena. In this work, we systematically assess the performance of single-reference algebraic diagrammatic construction combined with state interaction (SI-ADC) for describing electronic structure in the presence of spin-orbit coupling. We find that second-order SI-ADC methods (SI-ADC(2)) achieve zero-field-splitting accuracies comparable to those of higher-level and more computationally demanding approaches, including variational four-component ADC and two-component ADC methods based on spin-orbit effective Hamiltonians. We further demonstrate the broad applicability of SI-ADC by evaluating a diverse range of spin-orbit-coupled properties, including electron affinities, ionization potentials, neutral excitation energies, core-ionization energies, and magnetic g-tensors, for systems ranging from small molecules to transition-metal complexes and f-block compounds. Across these applications, SI-ADC(2) methods provide consistently accurate results, likely benefiting in part from favorable error cancellation between electron-correlation and spin-orbit effects. In contrast, SI-ADC(3) methods are generally less accurate, particularly for systems containing transition-metal and heavy elements. Overall, these results establish SI-ADC as an efficient and broadly applicable framework for incorporating spin-orbit coupling into ADC calculations of electronic and spectroscopic properties.