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Electronic and magnetic properties of the charge ordered phase of LuFe 2 O 4 are investigated by means of x-ray spectroscopic and theoretical electronic structure approaches. LuFe 2 O 4 is a compound showing fascinating magnetoelectric coupling via charge ordering. Here, we identify the spin ground state of LuFe 2 O 4 in the charge ordered phase to be a 2:1 ferrimagnetic configuration, ruling out a frustrated magnetic state. An enhanced orbital moment may enhance the magnetoelectric coupling. Furthermore, we determine the densities of states and the corresponding correlation potentials by means of x-ray photoelectron and emission spectroscopies, as well as electronic structure calculations. DOI: 10.1103/PhysRevB.80.220409 PACS number͑s͒: 75.80.ϩq, 71.20.Ϫb, 78.70.Dm, 78.70.En Multiferroic transition metal oxides, i.e., compounds in which more than one ferroic phase coexist, have gained enormous attention during the last few years. 1-4 Besides a number of perovskites and related compounds, 2,5,6 the charge frustrated layered compound LuFe 2 O 4 has attracted intense interest due to its fascinating ferroelectric and magnetoelectric properties. 7,8 LuFe 2 O 4 has a rhombohedral crystal structure ͑space group R3m͒. The underlying layered structure consists of W-like hexagonal Fe 2 O 2.5 and U-like LuO 1.5 layers. 9 The W layers comprise two triangular nets of Fe ions; the resulting electric polarization is induced via a frustrated charge ordering of Fe 2+ and Fe 3+ ions on the resulting honeycomb lattice below 330 K. [10][11][12] Below 240 K a longrange ferrimagnetic order sets in. 7 The fact that the ferroelectricity is caused by correlated electrons from the Fe ions leads to unusual properties and unique capabilities of LuFe 2 O 4 . A large response of the dielectric constant by applying small magnetic fields has been found, opening a possible route for future devices. 8 Phase transitions from the charge ordered ͑CO͒ phase have been very recently associated with a nonlinear current-voltage behavior and an electric-field-induced phase transition, which might be of interest for potential electric-pulse-induced resistive switching applications. 13,14 The large magnetoelectric coupling has been attributed to an intricate interplay between charge and spin degrees of freedom with the crystal lattice and external electrical and magnetic fields to some extent on a short-range order. [15][16][17][18][19] However, there is still some confusion about the nature of spin-charge coupling in LuFe 2 O 4 . In particular a model finding a ͱ 3 ϫ ͱ 3 CO ground state 20,21 is challenged by simulations implying that the electrical polarization in LuFe 2 O 4 is due to spin-charge coupling and a spin frustrated magnetic ground state in a chain CO state. 22,23 On the other hand the first model finds a ferrimagnetic spin ground state where Fe 2+ and 1/3 of Fe 3+ make up the majority spin, and 2/3 of Fe 3+ make up the minority spin.X-ray magnetic circular dichroism ͑XMCD͒ is a very powerful tool to investigate the internal magnetic stru...

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We report a comprehensive study of the electronic and magnetic properties of a star-shaped molecule comprising a MnII4O6 core. One feature of this compound is weak magnetic coupling constants compared to other similar polyoxo compounds. This leads to complicated low-lying magnetic states in which the ground state is not well separated from the upper-lying states, yielding a high-spin molecule with a giant magnetic moment of up to 20 microB/formula unit. We apply X-ray diffraction and magnetometry as well as other X-ray spectroscopic techniques, namely, X-ray photoelectron spectroscopy, X-ray magnetic circular dichroism, and X-ray emission spectroscopy. We compare our experimental results with ab initio electronic band structure calculations as well as the localized electronic structure around the Mn2+ ions with charge-transfer multiplet calculations.

Molecular magnets incorporate transition-metal ions with organic groups providing a bridge to mediate magnetic exchange interactions between the ions. Among them are star-shaped molecules in which antiferromagnetic couplings between the central and peripheral atoms are predominantly present. Those configurations lead to an appreciable spin moment in the nonfrustrated ground state. In spite of its topologically simple magnetic structure, the [Cr(III)Mn(II)(3) (PyA)(6)Cl(3)] (CrMn(3)) molecule, in which PyA represents the monoanion of syn-pyridine-2-aldoxime, exhibits nontrivial magnetic properties, which emerge from the combined action of single-ion anisotropy and frustration. In the present work, we elucidate the underlying electronic and magnetic properties of the heteronuclear, spin-frustrated CrMn(3) molecule by applying X-ray magnetic circular dichroism (XMCD), as well as magnetization measurements in high magnetic fields, density functional theory, and ligand-field multiplet calculations. Quantum-model calculations based on a Heisenberg Hamiltonian augmented with local anisotropic terms enable us not only to improve the accuracy of the exchange interactions but also to determine the dominant local anisotropies. A discussion of the various spin Hamiltonian parameters not only leads to a validation of our element selective transition metal L edge XMCD spin moments at a magnetic field of 5 T and a temperature of 5 K but also allows us to monitor an interesting effect of anisotropy and frustration of the manganese and chromium ions.