Importance of the many-body effects on the structural properties of the novel iron oxide Fe2O.

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.

Tunable Single-Atomic Charges on a Cleaved Intercalated Transition Metal Dichalcogenide.

Control of a single ionic charge state by altering the number of bound electrons has been considered as an ultimate testbed for atomic charge-induced interactions and manipulations, and such subject has been studied in artificially deposited objects on thin insulating layers. We demonstrate that an entire layer of controllable atomic charges on a periodic lattice can be obtained by cleaving metallic Co1/3NbS2, an intercalated transition metal dichalcogenide. We identified a metastable charge state of Co with a different valence and manipulated atomic charges to form a linear chain of the metastable charge state. Density functional theory investigation reveals that the charge state is stable due to a modified crystal field at the surface despite the coupling between NbS2 and Co via a1g orbitals. The idea can be generalized to other combinations of intercalants and base matrices, suggesting that they can be a new platform to explore single-atom-operational 2D electronics/spintronics.

Dimerization in α-TiCl3and α-TiBr3: the DFT study.

A series of DFT calculations for two layered compounds with honeycomb lattice-α-TiCl3and α-TiBr3has been performed. It was shown that the symmetric SU(4) spin-orbital model recently proposed ford1systems with honeycomb lattice cannot be realized in these titanates because they dimerize in the low temperature phase. This explains experimentally observed drop in magnetic susceptibility of α-TiBr3. Our results also suggest formation of valence-bond liquid state in the high-temperature phase of α-TiCl3and α-TiBr3.

Na9 Bi5 Os3 O24 : A Diamagnetic Oxide Featuring a Pronouncedly Jahn-Teller-Compressed Octahedral Coordination of Osmium(VI).

The Jahn-Teller (JT) theorem constitutes one of the most fundamental concepts in chemistry. In transition-element chemistry, the 3d4 and 3d9 configurations in octahedral complexes are particularly illustrative, where a distortion in local geometry is associated with a reduction of the electronic energy. However, there has been a lasting debate about the fact that the octahedra are found to exclusively elongate. In contrast, for Na9 Bi5 Os3 O24 , the octahedron around Os6+ (5d2 ) is heavily compressed, lifting the degeneracy of the t2g set of 5d orbitals such that in the sense of a JT compression a diamagnetic ground state results. This effect is not forced by structural constraints, the structure offers sufficient space for osmium to shift the apical oxygen atoms to a standard distance. The relevance of these findings is far reaching, since they provide new insights in the hierarchy of perturbations defining ground states of open shell electronic systems.

Orbital Effects in Solids: Basics, Recent Progress, and Opportunities.

The properties of transition metal compounds are largely determined by nontrivial interplay of different degrees of freedom: charge, spin, lattice, and also orbital ones. Especially rich and interesting effects occur in systems with orbital degeneracy. For example, they result in the famous Jahn-Teller effect, leading to a plethora of consequences for static and dynamic properties, including nontrivial quantum effects. In the present review, we discuss the main phenomena in the physics of such systems, paying central attention to the novel manifestations of those. After shortly summarizing the basic phenomena and their descriptions, we concentrate on several specific directions in this field. One of them is the reduction of effective dimensionality in many systems with orbital degrees of freedom due to the directional character of orbitals, with the concomitant appearance of some instabilities that lead in particular to the formation of dimers, trimers, and similar clusters in a material. The properties of such cluster systems, which are largely determined by their orbital structure, are discussed in detail, and many specific examples of those in different materials are presented. Another big field that has acquired special significance relatively recently is the role of the relativistic spin-orbit interaction. The mutual influence of this interaction and the more traditional Jahn-Teller physics is treated in detail in the second part of the review. In discussing all of these questions, special attention is paid to novel quantum effects.

Influence of Molecular Orbitals on Magnetic Properties of [x].

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 FeO 2 H x , 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 FeO 2 with strongly hybridized Fe- t 2 g -O- p z 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 FeO 2 , whereas strong ferromagnetic (FM) fluctuations were observed for FeO 2 H.

Old puzzle of incommensurate crystal structure of calaverite AuTe2 and predicted stability of novel AuTe compound.

Gold is a very inert element, which forms relatively few compounds. Among them is a unique material-mineral calaverite, [Formula: see text] Besides being the only compound in nature from which one can extract gold on an industrial scale, it is a rare example of a natural mineral with incommensurate crystal structure. Moreover, it is one of few systems based on Au, which become superconducting (at elevated pressure or doped by Pd and Pt). Using ab initio calculations we theoretically explain these unusual phenomena in the picture of negative charge-transfer energy and self-doping, with holes being largely in the Te [Formula: see text] bands. This scenario naturally explains incommensurate crystal structure of [Formula: see text], and it also suggests a possible mechanism of superconductivity. An ab initio evolutionary search for stable compounds in the Au-Te system confirms stability of [Formula: see text] and [Formula: see text] and leads to a prediction of an as yet unknown stable compound AuTe, which until now has not been synthesized.

Spectral and magnetic properties of Na2RuO3.

We present measurements of resistivity, x-ray absorption (XAS) and emission (XES) spectroscopy together with ab initio band structure calculations for quasi two dimensional ruthenate Na2RuO3. Density function calculations (DFT) and XAS and XES spectra both show that Na2RuO3 is a semiconductor with an activation energy of ∼80 meV. Our DFT calculations reveal large magneto-elastic coupling in Na2RuO3 and predict that the ground state of Na2RuO3 should be antiferromagnetic zig-zag.

Spin-singlet Quantum Ground State in Zigzag Spin Ladder Cu(CF3 COO)2.

The copper salt of trifluoroacetic acid, Cu(CF3 COO)2 , offers a new platform to investigate the quantum ground states of low-dimensional magnets. In practice, it realizes the ideal case of a solid hosting essentially isolated magnetic monolayers. These entities are constituted by well-separated two-leg half-integer spin ladders organized in a zigzag fashion. The ladders are comprised of dimeric units of edge-sharing tetragonal pyramids coupled through carbon ions. The spin-gap state in this compound was revealed by static and dynamic magnetic measurements. No indications of long range magnetic ordering down to liquid helium temperature were obtained in specific heat measurements. First principles calculations allow estimation of the main exchange interaction parameters, J⊥ =176 K and J∥ =12 K, consistent with the weakly interacting dimers model.

Covalent bonds against magnetism in transition metal compounds.

Magnetism in transition metal compounds is usually considered starting from a description of isolated ions, as exact as possible, and treating their (exchange) interaction at a later stage. We show that this standard approach may break down in many cases, especially in 4d and 5d compounds. We argue that there is an important intersite effect-an orbital-selective formation of covalent metal-metal bonds that leads to an "exclusion" of corresponding electrons from the magnetic subsystem, and thus strongly affects magnetic properties of the system. This effect is especially prominent for noninteger electron number, when it results in suppression of the famous double exchange, the main mechanism of ferromagnetism in transition metal compounds. We study this mechanism analytically and numerically and show that it explains magnetic properties of not only several 4d-5d materials, including Nb2O2F3 and Ba5AlIr2O11, but can also be operative in 3d transition metal oxides, e.g., in CrO2 under pressure. We also discuss the role of spin-orbit coupling on the competition between covalency and magnetism. Our results demonstrate that strong intersite coupling may invalidate the standard single-site starting point for considering magnetism, and can lead to a qualitatively new behavior.

Pressure-induced magnetic transitions with change of the orbital configuration in dimerised systems.

We suggest a possible scenario for magnetic transition under pressure in dimerised systems where electrons are localised on molecular orbitals. The mechanism of transition is not related with competition between kinetic energy and on-site Coulomb repulsion as in Mott-Hubbard systems, or between crystal-field splitting and intra-atomic exchange as in classical atomic spin-state transitions. Instead, it is driven by the change of bonding-antibonding splitting on part of the molecular orbitals. In the magnetic systems with few half-filled molecular orbitals external pressure may result in increase of the bonding-antibonding splitting and localise all electrons on low-lying molecular orbitals suppressing net magnetic moment of the system. We give examples of the systems, where this or inverse transition may occur and by means of ab initio band structure calculations predict that it can be observed in α-MoCl4 at pressure P ~ 11 GPa.

Valence states and possible charge ordering in LaCo(1-x)Rh(x)O3.

An unusual effect was discovered in Li et al (2010 J. Solid State Chem. 183 1388): the substitution of nonmagnetic low-spin Co(3+) in LaCoO3 by the formally isoelectronic and also nonmagnetic Rh(3+) led, surprisingly, to a rapid appearance of magnetism in LaCo(1-x)Rh(x)O3, even for small amounts of doping. Different explanations for this effect were proposed in the literature. To clarify the situation we carried out unbiased ab initio calculations of this system. We concluded that, in agreement with the original assumption of Li et al, but in contrast with later statements (Knizek et al 2012 Phys. Rev. B 85 134401), this effect is caused by the valence change ('redox reaction') Co(3+) + Rh(3+) → Co(2+) + Rh(4+), which creates magnetic Co(2+) and Rh(4+) ions. For the half-filled case LaCo1/2Rh1/2O3 we obtained the state with charge ordering of Co(2+) and Rh(4+) ions, which according to our calculations are antiferromagnetically coupled. The obtained results reasonably explain the observed behavior of the magnetic susceptibility of LaCo(1-x)Rh(x)O3, and the novel state predicted at half-doping could be verified experimentally by detailed structural and magnetic studies and by x-ray absorption spectroscopy.

Successive spin orderings of tungstate-bridged Li2Ni(WO4)2 of spin 1.

Magnetic, thermodynamic, and dielectric properties of Li2Ni(WO4)2 of S = 1 system have been studied using magnetic susceptibility, specific heat, and dielectric constant measurements. The magnetic orderings can be identified in three stages, including a short range magnetic ordering indicated by the rounded χ(T) peak with maximum at ∼20 K, and signatures of two successful antiferromagnetic long range orderings near T(N1) ~ 18 K and T(N2) ~ 13 K revealed by the d(χ(T)) /d(T) peaks. The successive long range magnetic orderings are related to the quasi triangular symmetry breaking in the ac- and bc-planes and to the change of the dielectric constant, suggesting the presence of spin-phonon coupling. The specific heat and magnetic entropy analysis for Li2Ni(WO4)2 shows the existence of a significant low dimensional magnetic correlations at high temperature and confirms the long range three-dimensional (3D) behavior of magnetic orderings below T(N1) and T(N2).

Magnetostriction and ferroelectric state in AgCrS2.

The band structure calculations in the GGA+U approximation show the presence of additional lattice distortions in the magnetically ordered phase of AgCrS2. The magnetostriction leads to the formation of long and short Cr-Cr bonds in the case when the respective Cr ions have the same or opposite spin projections. These changes in the Cr lattice are accompanied by distortions of the CrS6 octahedra, which in turn lead to the development of spontaneous electric polarization.

Electric field control of the magnetic chiralities in ferroaxial multiferroic RbFe(MoO4)2.

The coupling of magnetic chiralities to the ferroelectric polarization in multiferroic RbFe(MoO4)2 is investigated by neutron spherical polarimetry. Because of the axiality of the crystal structure below T(c)=190 K, helicity and triangular chirality are symmetric-exchange coupled, explaining the onset of the ferroelectricity in this proper-screw magnetic structure--a mechanism that can be generalized to other systems with ferroaxial distortions in the crystal structure. With an applied electric field, we demonstrate control of the chiralities in both structural domains simultaneously.