Relativistic Douglas-Kroll-Hess Calculations of Hyperfine Interactions within First Principles Multireference Methods

TL;DR

This paper implements a relativistic hyperfine interaction Hamiltonian based on Douglas-Kroll-Hess theory within multireference methods, enabling accurate calculations of hyperfine parameters for atomic, molecular, and large single-molecule magnets, highlighting the importance of relativistic effects.

Contribution

The paper introduces a second-order relativistic hyperfine Hamiltonian within multireference methods, improving the accuracy of hyperfine interaction calculations for heavy elements and complex molecules.

Findings

Relativistic correction reduces Fermi contact contribution, especially for heavier nuclei.

Active space size convergence improves agreement with experimental data.

Relativistic effects are crucial for accurate hyperfine parameters in large Tb-based SMMs.

Abstract

Relativistic magnetic hyperfine interaction Hamiltonian based on the Douglas-Kroll-Hess (DKH) theory up to the second order is implemented within the ab initio multireference methods including spin-orbit coupling in the Molcas/OpenMolcas package. This implementation is applied to calculate relativistic hyperfine coupling (HFC) parameters for atomic systems and diatomic radicals with valence s or d orbitals by systematically varying active space size in the restricted active space self-consistent field (RASSCF) formalism with restricted active space state interaction (RASSI) for spin-orbit coupling. The DKH relativistic treatment of the hyperfine interaction reduces the Fermi contact contribution to the HFC due to the presence of kinetic factors that regularize the singularity of the Dirac delta function in the nonrelativitic Fermi contact operator. This effect is more prominent for heavier nuclei. As the active space size increases, the relativistic correction of the Fermi contact contribution converges well to the experimental data for light and moderately heavy nuclei. The relativistic correction, however, does not significantly affect the spin-dipole contribution to the hyperfine interaction. In addition to the atomic and molecular systems, the implementation is applied to calculate the relativistic HFC parameters for large trivalent and divalent Tb-based single-molecule magnets (SMMs) such as Tb(III)Pc$_2$ and Tb(II)(Cp$^\text{iPr5}$)$_2$ without ligand truncation using well-converged basis sets. In particular, for the divalent SMM which has an unpaired valence 6s/5d hybrid orbital, the relativistic treatment of HFC is crucial for a proper description of the Fermi contact contribution. Even with the relativistic hyperfine Hamiltonian, the divalent SMM is shown to exhibit strong tunability of HFC via an external electric field (i.e., strong hyperfine Stark effect).