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We investigate how different chemical environment influences magneticproperties of terbium(III) (Tb)-based single-molecule magnets (SMMs), usingfirst-principles relativistic multireference methods. Recent experiments showedthat Tb-based SMMs can have exceptionally large magnetic anisotropy and thatthey can be used for experimental realization of quantum informationapplications, with a judicious choice of chemical environment. Here, we performcomplete active space self-consistent field (CASSCF) calculations includingrelativistic spin-orbit interaction (SOI) for representative Tb-based SMMs suchas TbPc$_2$ and TbPcNc in three charge states. We calculate low-energyelectronic structure from which we compute the Tb crystal-field parameters andconstruct an effective pseudospin Hamiltonian. Our calculations show thatligand type and fine points of molecular geometry do not affect the zero-fieldsplitting, while the latter varies weakly with oxidation number. On the otherhand, higher-energy levels have a strong dependence on all thesecharacteristics. For neutral TbPc$_2$ and TbPcNc molecules, the Tb magneticmoment and the ligand spin are parallel to each other and the coupling strengthbetween them does not depend much on ligand type and details of atomicstructure. However, ligand distortion and molecular symmetry play a crucialrole in transverse crystal-field parameters which lead to tunnel splitting. Thetunnel splitting induces quantum tunneling of magnetization by itself or bycombining with other processes. Our results provide insight into mechanisms ofmagnetization relaxation in the representative Tb-based SMMs.

Multireference Ab Initio Studies of Magnetic Properties of Terbium-Based Single-Molecule Magnets