Spin-reversal energy barriers of 305 K for Fe${}^{2+}$ $d^6$ ions with linear ligand coordination

Abstract

A remarkably large magnetic anisotropy energy of 305 K is computed by quantum chemistry methods for divalent Fe${}^{2+}$ $d^6$ substitutes at Li-ion sites with $D_{6h}$ point-group symmetry within the solid-state matrix of Li${}_3$N. This is similar to values calculated by the same approach and confirmed experimentally for linearly coordinated monovalent Fe${}^{1+}$ $d^7$ species, among the largest so far in the research area of single-molecule magnets. Our ab initio results therefore mark a new exciting exploration path in the search for superior single-molecule magnets, rooted in the $d_{xy}^{1.5}{d}_{x^2-y^2}^{1.5}{d}_{z^2}^1{d}_{yz}^1{d}_{zx}^1$ configuration of $d^6$ transition-metal ions with linear or quasilinear nearest-neighbor coordination. This $d^6$ axial anisotropy may be kept robust even for symmetries lower than $D_{6h}$, provided the ligand and farther-neighbor environment is engineered such that the $d_{xy}^{1.5}{d}_{x^2-y^2}^{1.5}{d}_{z^2}^1{d}_{yz}^1{d}_{zx}^1$ - $d_{xy}^1{d}_{x^2-y^2}^1{d}_{z^2}^2{d}_{yz}^1{d}_{zx}^1$ splitting remains large enough.

5 pages, 1 figure

References in corpus (1)

• Alternating magnetic anisotropy of Li${}_2$(Li${}_{1-x}{T}_x$)N with $T$ = Mn, Fe, Co, and Ni

Cited by in corpus (4)

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• Time-dependent spintronic anisotropy in magnetic molecules
• Cooperative quantum tunneling of the magnetization in Fe-doped Li${}_3$N
• Interplay of electron correlations, spin-orbit couplings, and structural effects for Cu centers in the quasi-two-dimensional magnet InCu${}_{2/3}$V${}_{1/3}$O${}_3$