Search

We study an interplay between the orbital degeneracy and the spin-orbit coupling (SOC) giving rise to spin-orbital entangled states in concentrated systems (cooperative Jahn-Teller [JT] effect). As a specific example, we analyze the interaction of electrons occupying triply degenerate single-ion t2g levels with trigonal vibrations (the t - T problem). A more general problem of the electron-lattice interaction involving both tetragonal and trigonal vibrations is also considered. It is shown that the result of such interaction crucially depends on the occupation of t2g levels leading to either the suppression or the enhancement of the JT effect by the SOC. © 2022 American Physical Society.

The state with effective total moment Jeff = 1/2 stabilized by the spin-orbit coupling is known to suppress Jahn-Teller distortions and may induce a strong exchange anisotropy. This in turn may lead to the formation of an elusive spin-liquid state in real materials. While recent studies have demonstrated that such a situation can be realized in 3d transition-metal compounds such as those based on Co2+ and Cu2+, diagnosis of Jeff = 1/2 state remains challenging. We show that resonant inelastic X-ray scattering is an effective tool to probe this state and apply it to CuAl2O4, material where Cu2+ ions were previously proposed to be in the Jeff = 1/2 state. Our results unambiguously demonstrate that, contrary to previous expectations, a competitive (to Jeff = 1/2) Jahn-Teller state realizes in this compound. © 2022, The Author(s).

In recent years, A-site ordered half-doped double-perovskite manganites RBaMn2O6 (R=rare earth) have attracted much attention due to their remarkable physical properties and a prospect of application as magnetoresistive, multiferroic, and oxygen storage materials. The nature of the ground state in RBaMn2O6 as well as sequence of phase transitions taking place at cooling are not yet well understood due to complexity in both experimental and theoretical studies. Here we address the origin of the ground-state structure in PrBaMn2O6 as well as its electronic and magnetic properties. Utilizing GGA+U approach and specially designed strategy to perform structural optimization, we show that the system has two competing AFM-A and AFM-CE magnetic structures with very close energies. The AFM-A structure is a metal, while AFM-CE is an insulator and the transition to the insulating state is accompanied by the charge Mn3+/Mn4+, and orbital 3x2 − r2/3y2 − r2 orderings. This orbital ordering results in strong cooperative Jahn-Teller (JT) distortions, which lower the crystal symmetry. Our findings give a key to understanding contradictions in available experimental data on PrBaMn2O6 and open up the prospects to theoretical refinements of ground-state structures in other RBaMn2O6 compounds. © 2022 Elsevier B.V.

The importance of many-body effects on the electronic and magnetic properties and stability of different structural phases was studied in novel iron oxide Fe2O. It was found that while Hubbard repulsion hardly affects the electronic spectrum of this material (m*/m ≈ 1.2), it strongly changes its phase diagram, shifting critical pressures of structural transitions to much lower values. Moreover, the P3̄m1 structure previously obtained in the density functional theory (DFT) becomes energetically unstable if many-body effects are taken into consideration. It is shown that these changes are due to magnetic moment fluctuations in the DFT+DMFT (method which combines density functional theory and dynamical mean-field theory) approach, which strongly modify the phase diagram of Fe2O. © 2022 The Royal Society of Chemistry

Based on the density functional theory, we examine the origin of ferromagnetism in the Weyl semimetal Co3Sn2S2 using different types of response theories. We argue that the magnetism of Co3Sn2S2 has a dual nature and bears certain aspects of both itineracy and localization. On the one hand, the magnetism is soft, where the local magnetic moments strongly depend on temperature and the angles formed by these moments at different Co sites of the kagome lattice, as expected for itinerant magnets. On the other hand, the picture of localized spins still remains adequate for the description of the local stability of the ferromagnetic (FM) order with respect to the transversal spin fluctuations. For the latter purposes, we employ two approaches, which provide quite different pictures for interatomic exchange interactions: the regular magnetic force theorem and a formally exact theory based on the calculation of the inverse response function. The exact theory predicts Co3Sn2S2 to be a three-dimensional ferromagnet with the strongest interaction operating between next-nearest neighbors in the adjacent kagome planes. The ligand states are found to play a very important role by additionally stabilizing the FM order. When the local moments decrease, the interplane interactions sharply decrease, first causing the FM order to become quasi-two-dimensional, and then making it unstable with respect to the spin-spiral order propagating perpendicular to the kagome plane. The latter instability is partly contributed by the states at the Fermi surface and may be relevant to the magnetic behavior of Co3Sn2S2 near the Curie temperature. Peculiarities of the half-metallic ferromagnetism in Co3Sn2S2 are also discussed. © 2022 American Physical Society.

The recently discovered material Cs3Fe2Br9 contains Fe2Br9 bi-octahedra forming triangular layers with hexagonal stacking along the c axis. In contrast to isostructural Cr-based compounds, the zero-field ground state is not a nonmagnetic S = 0 singlet-dimer state. Instead, the Fe2Br9 bi-octahedra host semiclassical S = 5/2 Fe3+ spins with a pronounced easy-axis anisotropy along c, and interestingly, the intradimer spins are ordered ferromagnetically. The high degree of magnetic frustration due to (various) competing intradimer and interdimer couplings leads to a surprisingly rich magnetic phase diagram. The zero-field ground state is already reached via an intermediate phase, and the high-field magnetization and thermal expansion data for H parallel to c identify 10 different ordered phases. Among them are phases with constant magnetization of 1/3, respectively 1/2, of the saturation value, and several transitions are strongly hysteretic with pronounced length changes, reflecting strong magnetoelastic coupling.

Structural properties of CuAl2O4, which was recently argued to show unusual suppression of the Jahn–Teller distortions by the spin–orbit coupling, are investigated under pressures up to 6 GPa. Analysis of x-ray powder diffraction experiments shows that CuAl2O4 gets unstable and decomposes onto CuO and Al2O3 at pressures ∼6 GPa and temperature ∼1000 K. This finding is complemented by the density-functional theory + U + spin–orbit coupling calculations, which demonstrate that this instability is partially driven by a (relatively) large compressibility of strongly Jahn–Teller distorted CuO. © 2020 IOP Publishing Ltd Printed in the UK.

The silver ruthenium oxide AgRuO3 consists of honeycomb Ru25+O62- layers and can be considered an analogue of SrRu2O6 with a different intercalation. We present measurements of magnetic susceptibility and specific heat on AgRuO3 single crystals, which reveal a sharp antiferromagnetic transition at 342(3) K. The electrical transport in single crystals of AgRuO3 is determined by a combination of activated conduction over an intrinsic semiconducting gap of ≈100 meV and carriers trapped and thermally released from defects. From powder neutron diffraction data a Néel-type antiferromagnetic structure with the Ru moments along the c axis is derived. Raman spectroscopy on AgRuO3 single crystals and muon spin rotation spectroscopy on powder samples indicate a further weak phase transition or a crossover in the temperature range 125-200 K. The transition does not show up in the magnetic susceptibility, and its origin is argued to be related to defects but cannot be fully clarified. The experimental findings are complemented by density-functional-theory-based electronic structure calculations. It is found that the magnetism in AgRuO3 is similar to that in SrRu2O6, however, with stronger intralayer and weaker interlayer magnetic exchange interactions. © 2021 authors. Published by the American Physical Society.

We have investigated the spin and oxidation states of Co in Co3BO5 using x-ray magnetic circular dichroism (XMCD) and dc magnetic susceptibility measurements. At low temperatures, XMCD experiments have been performed at the Co K-edge in Co3BO5 and Co2FeBO5 single crystals in the fully ferrimagnetically ordered phase. The Co (K-edge) XMCD signal is found to be related to the Co2+ magnetic sublattices in both compounds, providing strong experimental support for the low-spin (LS) Co3+ scenario. The paramagnetic susceptibility is highly anisotropic. An estimation of the effective magnetic moment in the temperature range 100-250 K correlates well with two Co2+ ions in the high-spin (HS) state and some orbital contribution, while Co3+ remains in the LS state. The crystal structure of the Co3BO5 single crystal has been solved in detail at the T range 296-703 K. The unit cell parameters and volume show anomalies at 500 and 700 K. The octahedral environment of the Co4 site strongly changes with heating. The generalized gradient approximation with Hubbard U correction calculations have revealed that, at low-temperatures, the system is insulating with a band gap of 1.4 eV, and the Co2+ ions are in the HS state, while Co3+ are in the LS state. At high temperatures (T > 700 K), the charge ordering disappears, and the system becomes metallic with all Co ions in 3d7 electronic configuration and HS state. © 2021 American Physical Society.

We have investigated the spin and oxidation states of Co in Co3BO5 using x-ray magnetic circular dichroism (XMCD) and dc magnetic susceptibility measurements. At low temperatures, XMCD experiments have been performed at the Co K-edge in Co3BO5 and Co2FeBO5 single crystals in the fully ferrimagnetically ordered phase. The Co (K-edge) XMCD signal is found to be related to the Co2+ magnetic sublattices in both compounds, providing strong experimental support for the low-spin (LS) Co3+ scenario. The paramagnetic susceptibility is highly anisotropic. An estimation of the effective magnetic moment in the temperature range 100–250 K correlates well with two Co2+ ions in the high-spin (HS) state and some orbital contribution, while Co3+ remains in the LS state. The crystal structure of the Co3BO5 single crystal has been solved in detail at the T range 296–703 K. The unit cell parameters and volume show anomalies at 500 and 700 K. The octahedral environment of the Co4 site strongly changes with heating. The generalized gradient approximation with Hubbard U correction calculations have revealed that, at low-temperatures, the system is insulating with a band gap of 1.4 eV, and the Co2+ ions are in the HS state, while Co3+ are in the LS state. At high temperatures (T > 700 K), the charge ordering disappears, and the system becomes metallic with all Co ions in 3d7 electronic configuration and HS state.

First-principles calculations and a model consideration of magnetically frustrated layered material PdCrO2 are performed. The results on the exchange parameters are in agreement with the experimental data on the Curie-Weiss temperature (θ). We show that experimentally observed strong suppression of the Néel temperature (TN) in comparison with the Curie-Weiss temperature is due to three main factors. First, as expected, this is connected with the layered structure and relatively small exchange interaction along the c axis. Second, deformation of the ideal in-plane 120° magnetic structure is crucial to provide finite TN value. However, these two factors are still insufficient to explain low TN and the large frustration factor |θ|/TN. Thus, we suggest a scenario of an exotic non-Fermi-liquid state in PdCrO2 above TN within the frameworks of the Anderson lattice model, which seems to explain qualitatively all its main peculiarities. © 2020 American Physical Society.

We study physical properties of layered α-ZrCl3 as a potential candidate for the physical realization of the SU(4) spin—orbital model. Both DFT and DFT + U + SOC calculations show that this material most probably dimerizes at normal conditions. Therefore, it is unlikely that the symmetric SU(4) model can be used for description of magnetic properties of α-ZrCl3 at low temperatures. In the dimerized structure electrons occupy molecular orbitals formed by the xy orbitals. One might expect a nonmagnetic ground state in this case. Interestingly the energy difference between various dimer packings is rather small and thus dimers may start to flow over the lattice as they do in Li2RuO3. © 2020, Pleiades Publishing, Inc.

MnSnTeO6, a new chiral antiferromagnet, was prepared both by topotactic transformation of the metastable rosiaite-type polymorph and by direct synthesis from coprecipitated hydroxides. Its structure and its static and dynamic magnetic properties were studied comprehensively both experimentally (through X-ray and neutron powder diffraction, magnetization, specific heat, dielectric permittivity, and ESR techniques) and theoretically (by means of ab initio density functional theory (DFT) calculations within the spin-polarized generalized gradient approximation). MnSnTeO6 is isostructural with MnSb2O6 (space group P321) and does not show any structural transition between 3 and 300 K. The magnetic susceptibility and specific heat exhibit an antiferromagnetic ordering at TN ≈ 9.8 K, which is confirmed by low-temperature neutron data. At the same time, the thermodynamic parameters demonstrate an additional anomaly on the temperature dependences of magnetic susceptibility χ(T), specific heat Cp(T) and dielectric permittivity ϵ(T) at T∗ ≈ 4.9 K, which is characterized by significant temperature hysteresis. Clear enhancement of the dielectric permittivity at T∗ is most likely to reflect the coupling of dielectric and magnetic subsystems leading to development of electric polarization. It was established that the ground state of MnSnTeO6 is stabilized by seven exchange parameters, and neutron diffraction revealed incommensurate magnetic structure with propagation vector k = (0, 0, 0.183) analogous to that of MnSb2O6. Ab initio DFT calculations demonstrate that the strongest exchange coupling occurs between planes along diagonals. All exchange parameters are antiferromagnetic and reveal moderate frustration. Copyright © 2020 American Chemical Society.

Investigation of the recently synthesized series of isostructural compounds Ba4NbTM3O12 (TM=Mn, Rh, and Ir) with transition-metal trimers in a face-sharing geometry makes it possible to examine a tendency to the molecular orbitals (MO) formation going from 3d to 5d transition metal ions. Our ab initio calculations of electronic and magnetic properties describe the experimental findings and demonstrate gradual transition from the picture of localized electrons for Mn to the MO picture for Rh and especially for Ir. We also show that the often used criterion, according to which the metal-metal distance in a compound shorter than in a respective metal always gives MO, may break down in some cases. © 2020 American Physical Society.

We measured the temperature dependence of low-frequency Raman spectra in Li2RuO3 and observed multipeak quasielastic scattering in the Ru honeycomb polarizations below and above the magnetostructural transition temperature. We attribute this scattering to the fluctuations of the energy density in the spin system. High-frequency electronic light scattering was observed at 2150cm-1. Its intensity increased significantly below the transition temperature, confirming substantial modification of the electronic structure due to removal of degeneracy in the t2g manifold of Ru4+ ions. © 2020 American Physical Society.

The Jahn-Teller effect is one of the most fundamental phenomena important not only for physics but also for chemistry and material science. Solving the Jahn-Teller problem and taking into account strong electron correlations we show that quantum entanglement of the spin and orbital degrees of freedom via spin-orbit coupling strongly affects this effect. Depending on the number of d electrons, it may quench (electronic configurations t2g2, t2g4, and t2g5), partially suppress (t2g1), or, in contrast, induce (t2g3) Jahn-Teller distortions. Moreover, in certain situations, interplay between the Jahn-Teller effect and spin-orbit coupling promotes formation of the "Mexican hat"energy surface facilitating various quantum phenomena. © 2020 authors.

Recent discoveries of various novel iron oxides and hydrides, which become stable at very high pressure and temperature, are extremely important for geoscience. In this paper, we report the results of an investigation on the electronic structure and magnetic properties of the hydride FeO2Hx, using density functional theory plus dynamical mean-field theory (DFT+DMFT) calculations. An increase in the hydrogen concentration resulted in the destruction of dimeric oxygen pairs and, hence, a specific band structure of FeO2 with strongly hybridized Fe-t2g-O-pz anti-bonding molecular orbitals, which led to a metallic state with the Fe ions at nearly 3+. Increasing the H concentration resulted in effective mass enhancement growth which indicated an increase in the magnetic moment localization. The calculated static momentum-resolved spin susceptibility demonstrated that an incommensurate antiferromagnetic (AFM) order was expected for FeO2, whereas strong ferromagnetic (FM) fluctuations were observed for FeO2H. © 2020 by the authors.