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Progress in magnetoelectric materials is hindered by apparently contradictory requirements for time-reversal symmetry broken and polar ferroelectric electronic structure in common ferromagnets and antiferromagnets. Alternative routes could be provided by recent discoveries of a time-reversal symmetry breaking anomalous Hall effect in noncollinear magnets and altermagnets, but hitherto reported bulk materials are not polar. Here, we report the observation of a spontaneous anomalous Hall effect in doped AgCrSe$_2$, a layered polar semiconductor with an antiferromagnetic coupling between Cr spins in adjacent layers. The anomalous Hall resistivity 3 $\mu\Omega$ cm is comparable to the largest observed in compensated magnetic systems to date, and is rapidly switched off when the angle of an applied magnetic field is rotated to $\sim 80^{\circ}$ from the crystalline $c$-axis. Our ionic gating experiments show that the anomalous Hall conductivity magnitude can be enhanced by modulating the $p$-type carrier density. We also present theoretical results that suggest the anomalous Hall effect is driven by Berry curvature due to noncollinear antiferromagnetic correlations among Cr spins, which are consistent with the previously suggested magnetic ordering in AgCrSe$_2$. Our results open the possibility to study the interplay of magnetic and ferroelectric-like responses in this fascinating class of materials., Comment: 8 pages, 5 figures

We report on the electronic band structure, structural, magnetic and thermal properties of Ce$_2$Rh$_3$Sn$_5$. Ce $L_{\mathrm{III}}$-edge XAS spectra give direct evidence for an intermediate valence behaviour. Thermodynamic measurements reveal magnetic transitions at $T_{\mathrm{N1}}\approx$ 2.9 K and $T_{\mathrm{N2}}\approx$ 2.4 K. Electrical resistivity shows behaviour typical for Kondo lattices. The coexistence of magnetic order and valence fluctuations in a Kondo lattice system we attribute to a peculiar crystal structure in which Ce ions occupy two distinct lattice sites. Analysis of the structural features of Ce$_2$Rh$_3$Sn$_5$, together with results of electronic band structure calculations and thermodynamic data indicate that Ce2 ions are in an intermediate valence state with the ground state electronic configuration close to 4$f^0$, whereas Ce1 ions are trivalent (4$f^1$) and contribute to the low temperature magnetic ordering. Thus, our joined experimental and theoretical investigations classify Ce$_2$Rh$_3$Sn$_5$ as a multivalent charge-ordered system., 12 pages with 10 figures (main manuscript) and 2 pages with 2 figures (supplementary information)

We report on the microscopic magnetic modeling of the spin-1/2 copper mineral malachite at ambient and elevated pressures. Despite the layered crystal structure of this mineral, the ambient-pressure susceptibility and magnetization data can be well described by an unfrustrated quasi-one-dimensional magnetic model. Weakly interacting antiferromagnetic alternating spin chains are responsible for a large spin gap of 120K. Although the intradimer Cu-O-Cu bridging angles are considerably smaller than the interdimer angles, density functional theory (DFT) calculations revealed that the largest exchange coupling of 190K operates within the structural dimers. The lack of the inversion symmetry in the exchange pathways gives rise to sizable Dzyaloshinskii-Moriya interactions which were estimated by full-relativistic DFT+U calculations. Based on available high-pressure crystal structures, we investigate the exchange couplings under pressure and make predictions for the evolution of the spin gap. The calculations evidence that intradimer couplings are strongly pressure-dependent and their evolution underlies the decrease of the spin gap under pressure. Finally, we assess the accuracy of hydrogen positions determined by structural relaxation within DFT and put forward this computational method as a viable alternative to elaborate experiments.

Magnetic susceptibility and microscopic magnetic model of the mineral clinoclase Cu3(AsO4)(OH)3 are reported. This material can be well described as a combination of two nonequivalent spin dimers with the sizable magnetic couplings of J about 700 K and J(D2) about 300 K. Based on density functional theory calculations, we pinpoint the location of dimers in the crystal structure. Surprisingly, the largest coupling operates between the structural Cu2O6 dimers. We investigate magnetostructural correlations in Cu2O6 structural dimers, by considering the influence of the hydrogen position on the magnetic coupling. Additionally, we establish the hydrogen positions that were not known so far and analyze the pattern of hydrogen bonding.

We apply neutron diffraction, high-resolution synchrotron x-ray diffraction, magnetization measurements, electronic structure calculations, and quantum Monte-Carlo simulations to unravel the structure and magnetism of (CuCl)LaTa2O7. Despite the pseudo-tetragonal crystallographic unit cell, this compound features an orthorhombic superstructure, similar to the Nb-containing (CuX)LaNb2O7 with X = Cl and Br. The spin lattice entails dimers formed by the antiferromagnetic fourth-neighbor coupling J(4), as well as a large number of nonequivalent interdimer couplings quantified by an effective exchange parameter J(eff). In (CuCl)LaTa2O7, the interdimer couplings are sufficiently strong to induce the long-range magnetic order with the Neel temperature T-N similar or equal to 7 K and the ordered magnetic moment of 0.53 mu(B), as measured with neutron diffraction. This magnetic behavior can be accounted for by J(eff)/J(4) similar or equal to 1.6 and J(4) similar or equal to 16 K. We further propose a general magnetic phase diagram for the (CuCl)LaNb2O7-type compounds, and explain the transition from the gapped spin-singlet (dimer) ground state in (CuCl)LaNb2O7 to the long-range antiferromagnetic order in (CuCl)LaTa2O7 and (CuBr)LaNb2O7 by an increase in the magnitude of the interdimer couplings J(eff)/J(4), with the (CuCl)LaM2O7 (M = Nb, Ta) compounds lying on different sides of the quantum critical point that separates the singlet and long-range-ordered magnetic ground states.

We present a comprehensive study of the crystal structure, magnetic structure, and microscopic magnetic model of (CuBr)LaNb2O7, the Br analog of the spin-gap quantum magnet (CuCl)LaNb2O7. Despite similar crystal structures and spin lattices, the magnetic behavior and even peculiarities of the atomic arrangement in the Cl and Br compounds are very different. The high-resolution x-ray and neutron data reveal a split position of Br atoms in (CuBr)LaNb2O7. This splitting originates from two possible configurations developed by [CuBr] zigzag ribbons. While the Br atoms are locally ordered in the 'ab' plane, their arrangement along the 'c' direction remains partially disordered. The predominant and energetically more favorable configuration features an additional doubling of the 'c' lattice parameter that was not observed in (CuCl)LaNb2O7. (CuBr)LaNb2O7 undergoes long-range antiferromagnetic ordering at TN=32 K, which is nearly 70% of the leading exchange coupling J4~48 K. The Br compound does not show any experimental signatures of low-dimensional magnetism, because the underlying spin lattice is three-dimensional. The coupling along the 'c' direction is comparable to the couplings in the 'ab' plane, even though the shortest Cu--Cu distance along 'c' (11.69 A) is three times larger than nearest-neighbor distances in the 'ab' plane (3.55 A). The stripe antiferromagnetic long-range order featuring columns of parallel spins in the 'ab' plane and antiparallel spins along 'c' is verified experimentally and confirmed by the microscopic analysis., Comment: Published version with the more positive title: 18 pages, 17 figures, 6 tables + Supplementary information

First thermoelectric properties measurements on bulk nanostructured Ba8Ga16Ge30 clathrate-I are presented. A sol-gel-calcination route was developed for preparing amorphous nanosized precursor oxides. The further reduction of the oxides led to quantitative yield of crystalline nanosized Ba8Ga16Ge30 clathrate-I. TEM investigations show the clathrate nanoparticles retain the size and morphology of the precursor oxides. The clathrate nanoparticles contain mainly thin plates (approx. 300 nm x 300 nm x 50 nm) and a small amount of nanospheres (diameter ~ 10 nm). SAED patterns confirm the clathrate-I structure type for both morphologies. The powders were compacted via Spark Plasma Sintering (SPS) to obtain a bulk nano-structured material. The Seebeck coefficient S, measured on low-density samples (53% of {\delta}x-ray), reaches -145 {\mu}V/k at 375 {\deg}C. The ZT values are quite low (0.02) due to the high resistivity of the sample (two orders of magnitude larger than bulk materials) and the low sample density. The trend of the temperature dependence of S is in agreement with the values obtained from electronic structure calculations and semi-classical Boltzmann transport theory within the constant scattering approximation. The total thermal conductivity (1.61 W/mK), measured on high density samples (93% of {\delta}x-ray), shows a reduction of 20-25% in relation to the bulk materials (2.1 W/mK). A further shaping of the sample for the Seebeck coefficient and electrical conductivity measurements was not possible due to the presence of cracks. An improvement on the design of the pressing tools, loading of the sample and profile of the applied pressure will enhance the mechanical stability of the samples. These investigations are now in progress., Comment: 21 pages, 10 figures

In a joint experimental and theoretical study, we investigate the isostructural collapse from the ambient pressure tetragonal phase to a collapsed tetragonal phase for non-superconducting metallic SrFe2As2 and SrFe_1.8Ru_0.2As_2. The crystallographic details have been studied using X-ray powder diffraction up to 20 GPa pressure in a diamond anvil cell. The structural phase transition occurs at 10 GPa and 9 GPa for SrFe2As2 and SrFe_1.8Ru_0.2As_2, respectively. The changes in the unit cell dimensions are highly anisotropic with a continuous decrease of the c lattice parameter with pressure, while the a-axis length increases until the transition to a collapsed tetragonal phase and then continues to decrease. Across the phase transition, we observe a volume reduction of 5% and 4% for SrFe2As2 and SrFe_1.8Ru_0.2As_2, respectively. We are able to discern that Ru substitution on the Fe-site acts like `chemical pressure' to the system. Density-functional theory-based calculations of the electronic structure and electron localizability indicator are consistent with the experimental observations. Detailed analysis of the electronic structure in k-space and real space reveals As 4pz interlayer bond formation as the driving force of the c/a collapse with a change in the As-As bond length of about 0.35ang., 10 pages, 7 figures

The spiral magnetic structure and underlying spin lattice of BiMnFe2O6 are investigated by low-temperature neutron powder diffraction and density functional theory band structure calculations. In spite of the random distribution of the Mn3+ and Fe3+ cations, this compound undergoes a transition into an incommensurate antiferromagnetically ordered state below TN ~ 220 K. The magnetic structure is characterized by the propagation vector k=[0,beta,0] with beta ~ 0.14 and the P22_12_11'(0 \beta 0)0s0s magnetic superspace symmetry. It comprises antiferromagnetic helixes propagating along the b-axis. The magnetic moments lie in the ac plane and rotate about pi*(1+beta) ~ 204.8 deg angle between the adjacent magnetic atoms along b. The spiral magnetic structure arises from the peculiar frustrated arrangement of exchange couplings in the ab plane. The antiferromagnetic coupling along the c-axis leads to the cancellation of electric polarization, and results in the lack of ferroelectricity in BiMnFe2O6., Comment: 11 pages, 8 figures, 8 tables

We report the crystal structure, magnetization measurements, and band-structure calculations for the spin-1/2 quantum magnet CaCu2(SeO3)2Cl2. The magnetic behavior of this compound is well reproduced by a uniform spin-1/2 chain model with the nearest-neighbor exchange of about 133 K. Due to the peculiar crystal structure, spin chains run in the direction almost perpendicular to the structural chains. We find an exotic regime of frustrated interchain couplings owing to two inequivalent exchanges of 10 K each. Peculiar superexchange paths grant an opportunity to investigate bond-randomness effects under partial Cl-Br substitution., Extended version: 9 pages, 7 figures, 4 tables

We apply density functional theory band structure calculations and quantum Monte Carlo simulations to investigate the Bose-Einstein condensation in the spin-1/2 quantum magnet Pb2V3O9. In contrast to previous conjectures on the one-dimensional nature of this compound, we present a quasi-two-dimensional model of spin dimers with ferromagnetic and antiferromagnetic interdimer couplings. Our model is well justified microscopically and provides a consistent description of the experimental data on the magnetic susceptibility, high-field magnetization, and field vs. temperature phase diagram. The Bose-Einstein condensation in the quasi-two-dimensional spin system of Pb2V3O9 is largely governed by intralayer interactions, whereas weak interlayer couplings have a moderate effect on the ordering temperature. The proposed computational approach is an efficient tool to analyze and predict high-field properties of quantum magnets., 6 pages, 6 figures, 1 table

We derive and investigate the microscopic model of the quantum magnet BiCu2PO6 using band structure calculations, magnetic susceptibility and high-field magnetization measurements, as well as ED and DMRG techniques. The resulting quasi-one-dimensional spin model is a two-leg AFM ladder with frustrating next-nearest-neighbor couplings along the legs. The individual couplings are estimated from band structure calculations and by fitting the magnetic susceptibility with theoretical predictions, obtained using ED. The nearest-neighbor leg coupling J1, the rung coupling J4, and one of the next-nearest-neighbor couplings J2 amount to 120-150 K, while the second next-nearest-neighbor coupling is J2'~J2/2. The spin ladders do not match the structural chains, and although the next-nearest-neighbor interactions J2 and J2' have very similar superexchange pathways, they differ substantially in magnitude due to a tiny difference in the O-O distances and in the arrangement of non-magnetic PO4 tetrahedra. An extensive ED study of the proposed model provides the low-energy excitation spectrum and shows that the system is in the strong rung coupling regime. The strong frustration by the next-nearest-neighbor couplings leads to a triplon branch with an incommensurate minimum. This is further corroborated by a strong-coupling expansion up to second order in the inter-rung coupling. Based on high-field magnetization measurements, we estimate the spin gap of 32 K and suggest the likely presence of antisymmetric DM anisotropy and inter-ladder coupling J3. We also provide a tentative description of the physics of BiCu2PO6 in magnetic field, in the light of the low-energy excitation spectra and numerical calculations based on ED and DMRG. In particular, we raise the possibility for a rich interplay between one- and two-component Luttinger liquid phases and a magnetization plateau at 1/2 of the saturation value.

We present a microscopic model of the spin-gap quantum magnet (CuCl)LaNb2O7 that was previously suggested as a realization of the spin-1/2 frustrated square lattice. Taking advantage of the precise atomic positions from recent crystal structure refinement, we evaluate individual exchange integrals and construct a minimum model that naturally explains all the available experimental data. Surprisingly, the deviation from tetragonal symmetry leads to the formation of spin dimers between fourth neighbors due to a Cu-Cl-Cl-Cu pathway with a leading antiferromagnetic exchange J4 ~ 25 K. The total interdimer exchange amounts to 12 - 15 K. Our model is in agreement with inelastic neutron scattering results and is further confirmed by quantum Monte-Carlo simulations of the magnetic susceptibility and the high-field magnetization. Our results establish (CuCl)LaNb2O7 as a non-frustrated system of coupled spin dimers with predominant antiferromagnetic interactions and provide a general perspective for related materials with unusual low-temperature magnetic properties., 4 pages, 4 figures, 1 table + supplementary

We report on band structure calculations and a microscopic model of the low-dimensional magnet beta-Cu2V2O7. Magnetic properties of this compound can be described by a spin-1/2 anisotropic honeycomb lattice model with the averaged coupling \bar J1=60-66 K. The low symmetry of the crystal structure leads to two inequivalent couplings J1 and J1', but this weak spatial anisotropy does not affect the essential physics of the honeycomb spin lattice. The structural realization of the honeycomb lattice is highly non-trivial: the leading interactions J1 and J1' run via double bridges of VO4 tetrahedra between spatially separated Cu atoms, while the interactions between structural nearest neighbors are negligible. The non-negligible inter-plane coupling Jperp~15 K gives rise to the long-range magnetic ordering at TN~26 K. Our model simulations improve the fit of the magnetic susceptibility data, compared to the previously assumed spin-chain models. Additionally, the simulated ordering temperature of 27 K is in remarkable agreement with the experiment. Our study evaluates beta-Cu2V2O7 as the best available experimental realization of the spin-1/2 Heisenberg model on the honeycomb lattice. We also provide an instructive comparison of different band structure codes and computational approaches to the evaluation of exchange couplings in magnetic insulators., 11 pages, 10 figures, 2 tables: revised version, extended description of simulation results

We report on the crystal structure of the quantum magnet (CuCl)LaNb2O7 that was controversially described with respect to its structural organization and magnetic behavior. Using high-resolution synchrotron powder x-ray diffraction, electron diffraction, transmission electron microscopy, and band structure calculations, we solve the room-temperature structure of this compound [alpha-(CuCl)LaNb2O7] and find two high-temperature polymorphs. The gamma-(CuCl)LaNb2O7 phase, stable above 640K, is tetragonal with a(sub) = 3.889 A, c(sub) = 11.738 A, and the space group P4/mmm. In the gamma-(CuCl)LaNb2O7 structure, the Cu and Cl atoms are randomly displaced from the special positions along the {100} directions. The beta-phase [a(sub) x 2a(sub) x c(sub), space group Pbmm] and the alpha-phase [2a(sub) x 2a(sub) x c(sub), space group Pbam] are stable between 640 K and 500 K and below 500 K, respectively. The structural changes at 500 K and 640 K are identified as order-disorder phase transitions. The displacement of the Cl atoms is frozen upon the gamma --> beta transformation, while a cooperative tilting of the NbO6 octahedra in the alpha-phase further eliminates the disorder of the Cu atoms. The low-temperature alpha-(CuCl)LaNb2O7 structure thus combines the two types of the atomic displacements that interfere due to the bonding between the Cu atoms and the apical oxygens of the NbO6 octahedra. The precise structural information resolves the controversy between the previous computation-based models and provides the long-sought input for understanding the magnetic properties of (CuCl)LaNb2O7., 12 pages, 10 figures, 5 tables; crystallographic information (cif files) included

Crystal structure and magnetic properties of the layered vanadium phosphate PbZnVO(PO4)2 are studied using x-ray powder diffraction, magnetization and specific heat measurements, as well as band structure calculations. The compound resembles AA'VO(PO4)2 vanadium phosphates and fits to the extended frustrated square lattice model with the couplings J(1), J(1)' between nearest-neighbors and J(2), J(2)' between next-nearest-neighbors. The temperature dependence of the magnetization yields estimates of averaged nearest-neighbor and next-nearest-neighbor couplings, J(1) ~ -5.2 K and J(2) ~ 10.0 K, respectively. The effective frustration ratio alpha=J(2)/J(1) amounts to -1.9 and suggests columnar antiferromagnetic ordering in PbZnVO(PO4)2. Specific heat data support the estimates of J(1) and J(2) and indicate a likely magnetic ordering transition at 3.9 K. However, the averaged couplings underestimate the saturation field, thus pointing to the spatial anisotropy of the nearest-neighbor interactions. Band structure calculations confirm the identification of ferromagnetic J(1), J(1)' and antiferromagnetic J(2), J(2)' in PbZnVO(PO4)2 and yield J(1)'-J(1) ~ 1.1 K in excellent agreement with the experimental value of 1.1 K, deduced from the difference between the expected and experimentally measured saturation fields. Based on the comparison of layered vanadium phosphates with different metal cations, we show that a moderate spatial anisotropy of the frustrated square lattice has minor influence on the thermodynamic properties of the model. We discuss relevant geometrical parameters, controlling the exchange interactions in these compounds, and propose a new route towards strongly frustrated square lattice materials., Comment: 14 pages, 9 figures, 5 tables

We report on the crystal structure of the quantum magnet CuClLaNb2O7 that was controversially described with respect to its structural organization and magnetic behavior. Using high-resolution synchrotron powder x-ray diffraction, electron diffraction, transmission electron microscopy, and band-structure calculations, we solve the room-temperature structure of this compound -CuClLaNb2O7 and find two high-temperature polymorphs. The -CuClLaNb2O7 phase, stable above 640 K, is tetragonal with asub=3.889 Å, csub =11.738 Å, and the space group P4/mmm. In the -CuClLaNb2O7 structure, the Cu and Cl atoms are randomly displaced from the special positions along the 100 directions. The phase asub2asubcsub, space group Pbmm and the phase 2asub2asubcsub, space group Pbam are stable between 640 K and 500 K and below 500 K, respectively. The structural changes at 500 and 640 K are identified as order-disorder phase transitions. The displacement of the Cl atoms is frozen upon the → transformation while a cooperative tilting of the NbO6 octahedra in the phase further eliminates the disorder of the Cu atoms. The low-temperature -CuClLaNb2O7 structure thus combines the two types of the atomic displacements that interfere due to the bonding between the Cu atoms and the apical oxygens of the NbO6 octahedra. The precise structural information resolves the controversy between the previous computation-based models and provides the long-sought input for understanding CuClLaNb2O7 and related compounds with unusual magnetic properties.

Over the last years, intermetallic compounds from the system Ce–Rh–Sn have attracted a considerable attention owing to a rich variety of strongly correlated electron phenomena they exhibit. CeRhSn2, Ce5Rh4Sn10, Ce2Rh3Sn5 and Ce3Rh4Sn13 are magnetically ordered heavy fermion systems [1-5]. Interestingly, for Ce3+xRh4Sn13-x (0.2

We have investigated the evolution, on doping, of the charge distribution in the new LaO1− xFxFeAs superconductor. This is done using 75As Nuclear Quadrupole Resonance (NQR), which is a sensitive local probe of the electric field gradient generated by the charge distribution. A significant increase of the quadrupole frequency is observed when going from the undoped situation to the superconducting region of the phase diagram, reflecting the change in density or spatial distribution of the electrons. This increase cannot be properly accounted for by LDA calculations, even though there is good agreement between theory and experience for the undoped case. We discuss this discrepancy as well as the relation to the superconductivity, i.e., the link to the doping-dependence of the critical temperature.

We present a computational study of the layered copper oxychloride [CuCl]LaNb(2)O(7) that has been recently proposed as a spin-1/2 frustrated square lattice compound. Our results evidence an orbitally degenerate ground state for the reported tetragonal crystal structure and reveal a Jahn-Teller-type structural distortion. This distortion heavily changes the local environment of copper -- CuO(2)Cl(2) plaquettes are formed instead of CuO(2)Cl(4) octahedra -- and restores the single-orbital scenario typical for copper oxides and oxyhalides. The calculated distortion is consistent with the available diffraction data and the experimental results on the electric field gradients for the Cu and Cl sites. The band structure suggests a complex three-dimensional spin model with the interactions up to the fourth neighbors. Despite the layered structure of (CuCl)LaNb(2)O(7), the spin system has pronounced one-dimensional features. Yet, sizable interchain interactions lead to the strong frustration and likely cause the spin-gap behavior. Computational estimates of individual exchange couplings are in qualitative agreement with the experimental data., 13 pages, 9 figures, 3 tables

The complex oxide Pb(0.55)Cd(0.45)V(2)O(5) was synthesized and investigated by means of X-ray powder diffraction, electron diffraction, magnetic susceptibility measurements and band structure calculations. Its structure is similar to that of MV(2)O(5) compounds (M = Na, Ca) giving rise to a spin system of coupled S=1/2 two-leg ladders. Magnetic susceptibility measurements reveal a spin gap-like behavior with \Delta ~ 270 K and a spin singlet ground state. Band structure calculations suggest Pb(0.55)Cd(0.45)V(2)O(5) to be a system of weakly coupled dimers in perfect agreement with the experimental data. Pb(0.55)Cd(0.45)V(2)O(5) provides an example of the modification of the spin system in layered vanadium oxides by cation substitution. Simple correlations between the cation size, geometrical parameters and exchange integrals for the MV(2)O(5)-type oxides are established and discussed., Comment: 8 pages, 7 figures