Valence and magnetic instabilities in Sm compounds at high pressures

We report on the study of the response to high pressures of the electronic and magnetic properties of several Sm-based compounds, which span at ambient pressure the whole range of stable charge states between the divalent and the trivalent. Our nuclear forward scattering of synchrotron radiation and specific heat investigations show that in both golden SmS and SmB6 the pressure-induced insulator to metal transitions (at 2 and about 4-7 GPa, respectively) are associated with the onset of long-range magnetic order, stable up to at least 19 and 26 GPa, respectively. This long-range magnetic order, which is characteristic of Sm(3+), appears already for a Sm valence near 2.7. Contrary to these compounds, metallic Sm, which is trivalent at ambient pressure, undergoes a series of pressure-induced structural phase transitions which are associated with a progressive decrease of the ordered 4f moment.Comment: 15 pages (including 7 figures) submitted to J. Phys.: Condens. Matte

Orbital-selective behavior in cubanite CuFe2S3

Using ab initio band structure calculations we show that mineral cubanite, CuFe2S3, demonstrates an orbital-selective behavior with some of the electrons occupying molecular orbitals of x2−y2 symmetry and others localized at atomic orbitals. This is a rare situation for 3d transition metal compounds that explains the experimentally observed absence of charge disproportionation, anomalous Mössbauer data, and ferromagnetic ordering in between nearest-neighbor Fe ions. ©2022 American Physical SocietyAAAA-A18-118020190095-4; Russian Science Foundation, RSF: 20-62-46047DFT calculations and their analysis was supported by the Russian Science Foundation via Project No. 20-62-46047, while analysis of Mossbauer data motivated this study was supported by the Russian Ministry of Science and High Education via program “Quantum” (No. AAAA-A18-118020190095-4). We also thank Prof. A. Fujimori for useful discussions on physical properties of this material

Enhanced dimerization of TiOCl under pressure: spin-Peierls - to - Peierls transition

We report high-pressure x-ray diffraction and magnetization measurements combined with ab-initio calculations to demonstrate that the high-pressure optical and transport transitions recently reported in TiOCl, correspond in fact to an enhanced Ti3+-Ti3+ dimerization existing already at room temperature. Our results confirm the formation of a metal-metal bond between Ti3+ ions along the b-axis of TiOCl, accompanied by a strong reduction of the electronic gap. The evolution of the dimerization with pressure suggests a crossover from the spin-Peierls to a conventional Peierls situation at high pressures.Comment: 9pages, 4 figure

Observation of insulator-metal transition in EuNiO3_{3} under high pressure

The charge transfer antiferromagnetic (T$_{N}$ =220 K) insulator EuNiO$_{3}$ undergoes, at ambient pressure, a temperature-induced metal insulator MI transition at T$_{MI}$=463 K. We have investigated the effect of pressure (up to p~20 GPa) on the electronic, magnetic and structural properties of EuNiO$_{3}$ using electrical resistance measurements, {151}^Eu nuclear resonance scattering of synchrotron radiation and x-ray diffraction, respectively. With increasing pressure we find at p$_{c}$ =5.8 GPa a transition from the insulating state to a metallic state, while the orthorhombic structure remains unchanged up to 20 GPa. The results are explained in terms of a gradual increase of the electronic bandwidth with increasing pressure, which results in a closing of the charge transfer gap. It is further shown that the pressure-induced metallic state exhibits magnetic order with a lowervalue of T$_{N}$ (T$_{N}$ ~120 K at 9.4 GPa) which disappears between 9.4 and 14.4 GPa.Comment: 10 pages, 3 figure

Pressure driven collapse of the magnetism in the Kondo insulator UNiSn

The effect of pressure on the electronic and magnetic properties of the antiferromagnetic (TN~43 K) narrow gap semiconductor UNiSn has been investigated by 119Sn Mössbauer spectroscopy and nuclear forward scattering of synchrotron radiation, electrical resistance, and x-ray diffraction. We show that the decrease of the semiconducting gap which leads to a metallic state at p~9 GPa is associated with an enhancement of TN. At higher pressures, both TN and the transferred magnetic hyperfine field decrease, with a collapse of magnetism at ~18.5 GPa. The results are explained by a volume-dependent competition between indirect Ruderman-Kittel-Kasuya-Yosida interaction and the 5f-ligand hybridization

Two-band second moment model and an interatomic potential for caesium

A semi-empirical formalism is presented for deriving interatomic potentials for materials such as caesium or cerium which exhibit volume collapse phase transitions. It is based on the Finnis-Sinclair second moment tight binding approach, but incorporates two independent bands on each atom. The potential is cast in a form suitable for large-scale molecular dynamics, the computational cost being the evaluation of short ranged pair potentials. Parameters for a model potential for caesium are derived and tested

Orbital-selective behavior in cubanite CuFe2S3

Using ab initio band structure calculations we show that mineral cubanite, CuFe2S3, demonstrates an orbital-selective behavior with some of the electrons occupying molecular orbitals of x(2) - y(2) symmetry and others localized at atomic orbitals. This is a rare situation for 3d transition metal compounds that explains the experimentally observed absence of charge disproportionation, anomalous Mossbauer data, and ferromagnetic ordering in between nearest-neighbor Fe ions