Magnetic anisotropy of tellurium(I) and selenium(I)† in a Li3N host crystal
Year: 2026
Type: preprint
Abstract: Magnetic anisotropy in low-coordinate main-group compounds has recently emerged as a promising route toward realizing single-molecule magnet behavior beyond traditional transition-metal and lanthanide systems. In this work, we investigate the electronic structure and magnetic properties of selenium-and tellurium-doped Li3N crystals using a combination of periodic density functional theory and embedded ionic-crystal QM/MM multireference calculations. Substitution of Li(1) sites by Se(I) and Te(I) generates low-coordinate np3 configurations embedded in a highly symmetric crystalline environment. Periodic calculations reveal substantial differences in spin localization and covalency between the two dopants: Te-doping stabilizes a spin-polarized electronic structure with localized magnetic character, whereas stronger Se 4p–N 2p hybridization leads to increased delocalization and a non-magnetic DFT ground state. Multireference SA-CASSCF/NEVPT2 calculations show that both systems possess magnetically isotropic ground states dominated by a singly occupied σ bonding orbital, while the first excited states exhibit pronounced axial magnetic anisotropy arising from nearly degenerate π∗ x and π∗ y orbitals coupled through spin–orbit interaction. For Te-doped clusters, extremely small transverse g-tensor components (gx,gy ≈ 0.002) and large axial components (gz ≈ 3.9) indicate near-ideal magnetic axiality, slightly stronger than in the Se analogues. The larger spin–orbit coupling of tellurium also produces significantly enhanced spin–orbit splitting relative to selenium. These results demonstrate that heavy main-group elements embedded in suitable low-coordinate environments can support highly anisotropic magnetic states and further support theoretical design principles for main-group single-molecule magnets.
Source: ChemRxiv
Authors: Dániel Nagy, Akseli Mansikkamäki
Language: English
Field: Materials Science
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W7212028576