Strong Relativistic Effects in Lanthanide-Based Single-Molecule Magnets.

Lanthanide-based single-molecule magnets (SMMs) are promising building blocks for quantum memory and spintronic devices. Designing lanthanide-based SMMs with long spin relaxation time requires a detailed understanding of their electronic structure, including the crucial role of the spin-orbit coupling (SOC). While traditional calculations of SOC using the perturbation theory applied to a solution of the nonrelativistic Schrödinger equation are valid for light atoms, this approach is questionable for systems containing heavy elements such as lanthanides. We investigate the accuracy of the perturbation estimates of SOC by variationally solving the Dirac equation for the [DyO]+ molecule, a prototype of a lanthanide-based SMM. We show that the energy splittings between the MJ states involved in spin relaxation depend on the interplay between strong SOC and dynamic electron correlation. We demonstrate that this interplay affects the resonances between the spin and vibrational transitions and, therefore, the spin relaxation time.