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The stability of the double-layered antiferromagnets and their magnonic properties are investigated by considering two model systems, the linear chain (LC) and more complex chain of railroad trestle (RT) geometry, and a real example of chromium nitride CrN. The spin-paired order ($\cdots{+}{+}{-}{-}\cdots$) in LC requires an alternation of the ferromagnetic and antiferromagnetic (AFM) interactions, while analogous spin-paired order in RT can be stable even for all magnetic exchange interactions being AFM. The rock-salt structure of CrN evokes clear magnetic frustration since Cr atoms in face-centered cubic lattice form links to twelve nearest neighbors all equivalent and AFM. Nonetheless, the magnetostructural transition to an orthorhombically distorted phase below $T_\text{N} = 287~\text{K}$ leads to a diversification of Cr-Cr links, which suppresses the frustration and allows for stable double-layered AFM order of CrN. Based on $\textit{ab initio}$ calculated exchange parameters, the magnon spectra and temperature evolution of ordered magnetic moments are derived., Comment: 7 pages, 8 figures

We present a detailed theoretical study of the electronic structure of hafnium tin HfSn crystallizing in a B$20$ structure, renowned for the diversity of physical and peculiar topological properties. The chiral crystal structure of these materials protects multifold band crossings located at high symmetry points. We employ density functional methods to reveal basic features of the band structure and Fermi surface topology of HfSn, on top of which an effective tight-binding model is built. The compound exhibits a fourfold band crossing pinned at the ${\Gamma}$ point. We investigate routes that can shift such crossings towards the Fermi level, offering a unique way to possibly tune the compound`s properties. Specifically, we show that the energy position of the fourfold crossing can be easily manipulated via external perturbations such as strain and pressure. Considering that this point carries a topological charge larger than one, such tuning is of great importance. We anticipate that the approach presented in the current study can be utilized to investigate symmetry protected crossings in a wide class of materials.

Based on our first detailed $^{181}$Ta nuclear quadrupole resonance (NQR) studies from 2017 on the Weyl semimetal TaP, we now extended our NQR studies to another Ta-based monopnictide TaAs. In the present work, we have determined the temperature-dependent $^{181}$Ta-NQR spectra, the spin-lattice relaxation time $T_{1}$, and the spin-spin relaxation time $T_{2}$. We found the following characteristic features that showed great contrast to what was found in TaP: (1) The quadrupole coupling constant and asymmetry parameter of EFG, extracted from three NQR frequencies, have a strong temperature dependence above $\sim$80 K that cannot be explained by the density functional theory calculation incorporating the thermal expansion of the lattice. (2) The temperature dependence of the spin-lattice relaxation rate, $1/T_{1} T$, shows a $T^{4}$ power law behavior above $\sim$30 K. This is a great contrast with the $1/T_{1} T \propto T^{2}$ behavior found in TaP, which was ascribed to the magnetic excitations at the Weyl nodes with a temperature-dependent orbital hyperfine coupling. (3) Regarding the nuclear spin-spin interaction, we found the spin-echo signal decays with the pulse separation simply by a Lorentzian function in TaAs, but we have observed spin-echo modulations in TaP that is most likely due to the indirect nuclear spin-spin coupling via virtually excited Weyl fermions. From our experimental findings, we conclude that the present NQR results do not show dominant contributions from Weyl fermion excitations in TaAs., Comment: 8 pages, 10 figures

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

The layered delafossite metal PdCrO$_2$ is a natural heterostructure of highly conductive Pd layers Kondo coupled to localized spins in the adjacent Mott insulating CrO$_2$ layers. At high temperatures $T$ it has a $T$-linear resistivity which is not seen in the isostructural but non-magnetic PdCoO$_2$. The strength of the Kondo coupling is known, as-grown crystals are extremely high purity and the Fermi surface is both very simple and experimentally known. It is therefore an ideal material platform in which to investigate 'Planckian metal' physics. We do this by means of controlled introduction of point disorder, measurement of the thermal conductivity and Lorenz ratio and studying the sources of its high temperature entropy. The $T$-linear resistivity is seen to be due mainly to elastic scattering and to arise from a sum of several scattering mechanisms. Remarkably, this sum leads to a scattering rate within 10$\%$ of the Planckian value of $k_BT/$$\hbar$.

Spatial inversion symmetry in crystal structures is closely related to the superconducting (SC) and magnetic properties of materials. Recently, several theoretical proposals that predict various interesting phenomena caused by the breaking of the local inversion symmetry have been presented. However, experimental validation has not yet progressed owing to the lack of model materials. Here we present evidence for antiferromagnetic (AFM) order in CeRh$_{2}$As$_{2}$ (SC transition temperature $T_{\rm SC} \sim 0.37$~K), wherein the Ce site breaks the local inversion symmetry. The evidence is based on the observation of different extents of broadening of the nuclear quadrupole resonance spectrum at two crystallographically inequivalent As sites. This AFM ordering breaks the inversion symmetry of this system, resulting in the activation of an odd-parity magnetic multipole. Moreover, the onset of antiferromagnetism $T_{\rm N}$ within an SC phase, with $T_{\rm N} < T_{\rm SC}$, is quite unusual in systems wherein superconductivity coexists or competes with magnetism. Our observations show that CeRh$_{2}$As$_{2}$ is a promising system to study how the absence of local inversion symmetry induces or influences unconventional magnetic and SC states, as well as their interaction., Comment: 6 pages, 3 figures, to be published in PRL

Applying in-plane uniaxial pressure to strongly correlated low-dimensional systems has been shown to tune the electronic structure dramatically. For example, the unconventional superconductor Sr$_2$RuO$_4$ can be tuned through a single Van Hove singularity which results in a strong enhancement of both $T_\text{c}$ and $H_\text{c2}$. Out-of-plane ($c$ axis) uniaxial pressure is expected to tune the quasi-two-dimensional structure even more strongly, causing it to approach two Van Hove singularities simultaneously. Here we achieve a record value of $3.2$ GPa compression along the $c$ axis of Sr$_2$RuO$_4$. Although the rise in $H_\text{c2}$ shows that we are indeed approaching the van Hove points, $T_\text{c}$ is suppressed, a result that contradicts expectations based on simple two-dimensional models. As a first attempt to take the third dimension into account, we present three-dimensional calculations in the weak interaction limit, and discuss the extent to which they are consistent with observation. Our experimental results highlight the importance of out-of-plane effects in low-dimensional systems in general and provide new constraints on theories of the pairing interaction in Sr$_2$RuO$_4$.

The magnetic, thermal and transport properties as well as electronic band structure of MnPtSi are reported. MnPtSi is a metal that undergoes a ferromagnetic transition at $T_{\mathrm{C}}=340$(1) K and a spin-reorientation transition at $T_{\mathrm{N}}=326$(1) K to an antiferromagnetic phase. First-principles electronic structure calculations indicate a not-fully polarized spin state of Mn in a $d^5$ electron configuration with $J=S=3$/2, in agreement with the saturation magnetization of 3~$\mu_{\mathrm{B}}$ in the ordered state and the observed paramagnetic effective moment. A sizeable anomalous Hall effect in the antiferromagnetic phase alongside the computational study suggests that the antiferromagnetic structure is non-collinear. Based on thermodynamic and resistivity data we construct a magnetic phase diagram. Magnetization curves $M$($H$) at low temperatures reveal a metamagnetic transition of spin-flop type. The spin-flopped phase terminates at a critical point with $T_{\mathrm{cr}}\approx 300$ K and $H_{\mathrm{cr}}\approx 10$ kOe, near which a peak of the magnetocaloric entropy change is observed. Using Arrott plot analysis and magnetoresistivity data we argue that the metamagnetic transition is of a first-order type, whereas the strong field dependence of $T_{\mathrm{N}}$ and the linear relationship of the $T_{\mathrm{N}}$ with $M^2$ hint at its magnetoelastic nature.

We present inelastic neutron scattering data on the quantum paramagnet AgVOAsO4 that establish the system is a S=1/2 alternating spin chain compound and provide a direct measurement of the spin gap. We also present experimental evidence for two different types of field-induced magnetic order between mu_0H_c1 = 8.4T and mu_0H_c2 = 48.9T, which may be related to Bose-Einstein condensation (BEC) of triplons. Thermodynamic measurements in magnetic fields up to 60T and temperatures down to 0.1K reveal a H-T phase diagram consisting of a dome encapsulating two ordered phases with maximum ordering temperatures of 3.8K and 5.3K respectively. This complex phase diagram is not expected for a single-Q BEC system and therefore establishes AgVOAsO4 as a promising multi-Q BEC candidate capable of hosting exotic vortex phases.

We present a detailed study of the temperature evolution of the crystal structure, specific heat, magnetic susceptibility and resistivity of single crystals of the paradigmatic valence-fluctuating compound EuIr$_2$Si$_2$. A comparison to stable-valent isostructural compounds EuCo$_2$Si$_2$ (with Eu$^{3+}$), and EuRh$_2$Si$_2$, (with Eu$^{2+}$) reveals an anomalously large thermal expansion indicative of the lattice softening associated to valence fluctuations. A marked broad peak at temperatures around 65-75 K is observed in specific heat, susceptibility and the derivative of resistivity, as thermal energy becomes large enough to excite Eu into a divalent state, which localizes one f electron and increases scattering of conduction electrons. In addition, the intermediate valence at low temperatures manifests in a moderately renormalized electron mass, with enhanced values of the Sommerfeld coefficient in the specific heat and a Fermi-liquid-like dependence of resistivity at low temperatures. The high residual magnetic susceptibility is mainly ascribed to a Van Vleck contribution. Although the intermediate/fluctuating valence duality is to some extent represented in the interconfiguration fluctuation model commonly used to analyze data on valence-fluctuating systems, we show that this model cannot describe the different physical properties of EuIr$_2$Si$_2$ with a single set of parameters., Comment: 12 pages, 4 figures, 1 table

We study the electronic structure of delafossite PtCoO$_2$ to elucidate its extremely small resistivity and high mobility. The band exhibits steep dispersion near the Fermi level despite the fact that it is formed mainly by Pt $d$ orbitals that are typically localized. We propose a picture based on two hidden kagome-lattice-like electronic structure: one originating from Pt $s+p_x/p_y$ orbitals, and the other from Pt $d_{3z^2-r^2}+d_{xy}/d_{x^2-y^2}$ orbitals, each placed on the bonds of the triangular lattice. In particular, we find that the underlying Pt $s+p_x/p_y$ bands actually determine the steepness of the original dispersion, so that the large Fermi velocity can be attributed to the large width of the Pt $s+p_x/p_y$ band. More importantly, the kagome-like electronic structure gives rise to "orbital-momentum locking" on the Fermi surface, which reduces the electron scattering by impurities. We conclude that the combination of the large Fermi velocity and the orbital-momentum locking is likely to be the origin of the extremely small resistivity in PtCoO$_2$., Comment: 9 pages, 14 figures

The two-dimensional (2D) metal PtCoO$_2$ is renowned for the lowest room temperature resistivity among all oxides, close to that of the top two materials Ag and Cu. In addition, we theoretically predict a strong intrinsic spin Hall effect. This originates from six strongly-tilted Dirac cones that we find in the electronic structure near the Fermi surface, where a gap is opened by large spin-orbit coupling (SOC). This is underpinned by rich topological properties; in particular, the phenomenology of a mirror Chern metal is realized not exactly, but very accurately, on account of an approximate crystalline symmetry. We expect that such 'vicinity topology' to be a feature of relevance well beyond this material. Our Wilson loop analysis indicates further elaborate features such as fragile topology. These findings highlight PtCoO$_2$ as a promising material for spintronic applications as well as a platform to study the interplay of symmetry and topology., Comment: 9 pages, 7 figures

The crystalline electric field (CEF) of Ce3+ in trigonal symmetry has recently become of some relevance, for instance, in the search of frustrated magnetic systems. Fortunately, it is one of the CEF case in which a manageable analytic solution can be obtained. Here, we present this solution for the general case, and use this result to determine the CEF scheme of the new compound CeIr3Ge7 with the help of T-dependent susceptibility and isothermal magnetization measurements. The resulting CEF parameters B20 = 34.4 K, B40 = 0.82 K and B43 = 67.3 K correspond to an exceptional large CEF splittings of the first and second excited levels, 374 K and 1398 K, and a large mixing between the +-|5/2> and the -+|1/2> states. This indicates a very strong easy plane anisotropy with an unusual small c-axis moment. Using the same general expressions, we show that the properties of the recently reported system CeCd3As3 can also be described by a similar CEF scheme, providing a much simpler explanation for its magnetic properties than the initial proposal. Moreover, a similar strong easy plane anisotropy has also been reported for the two compounds CeAuSn and CePdAl4Ge2, indicating that the CEF scheme elaborated here for CeIr3Ge7 corresponds to an exemplary case for Ce3+ in trigonal symmetry., Comment: 10 pages, 7 figures

We have studied magneto transport in the single-band, quasi-two-dimensional metals PdCoO2 and PtCoO2, which have extremely long mean free paths. We observer a strong temperature dependence of the Hall resistivity in small applied, fields, linked to a large violation of Kohler's rule in the magnetoresistance. We discuss the extent to which these observations can be accounted for by standard transport theory, and describe other possible, unconventional contributions to magnetotransport in very high purity metals.

We report on a combined study of the de Haas-van Alphen effect and angle resolved photoemission spectroscopy on single crystals of the metallic delafossite PdRhO$_2$ rounded off by \textit{ab initio} band structure calculations. A high sensitivity torque magnetometry setup with SQUID readout and synchrotron-based photoemission with a light spot size of $~50\,\mu\mathrm{m}$ enabled high resolution data to be obtained from samples as small as $150\times100\times20\,(\mu\mathrm{m})^3$. The Fermi surface shape is nearly cylindrical with a rounded hexagonal cross section enclosing a Luttinger volume of 1.00(1) electrons per formula unit.

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., Comment: 12 pages with 10 figures (main manuscript) and 2 pages with 2 figures (supplementary information)

In this joint experimental and theoretical work magnetic properties of the Cu$^{2+}$ mineral szenicsite Cu$_3$(MoO$_4$)(OH)$_4$ are investigated. This compound features isolated triple chains in its crystal structure, where the central chain involves an edge-sharing geometry of the CuO$_4$ plaquettes, while the two side chains feature a corner-sharing zig-zag geometry. The magnetism of the side chains can be described in terms of antiferromagnetic dimers with a coupling larger than 200 K. The central chain was found to be a realization of the frustrated antiferromagnetic $J_1$-$J_2$ chain model with $J_1\simeq 68$ K and a sizable second-neighbor coupling $J_2$. The central and side chains are nearly decoupled owing to interchain frustration. Therefore, the low-temperature behavior of szenicsite should be entirely determined by the physics of the central frustrated $J_1$-$J_2$ chain. Our heat-capacity measurements reveal an accumulation of entropy at low temperatures and suggest a proximity of the system to the Majumdar-Ghosh point of the antiferromagnetic $J_1$-$J_2$ spin chain, $J_2/J_1=0.5$.

Cuprate materials, like those hosting high temperature superconductivity, represent a famous class of materials where the correlations between the strongly entangled charges and spins produce complex phase diagrams. Several years ago the Zhang-Rice singlet was proposed as a natural quasiparticle in hole-doped cuprates. The occurance and binding energy of this quasiparticle, consisting of a pair of bound holes with antiparallel spins on the same CuO$_4$ plaquette, depends on the local electronic interactions, which are fundamental quantities for understanding the physics of the cuprates. Here, we employ state-of-the-art Resonant Inelastic X-ray Scattering (RIXS) to probe the correlated physics of the CuO$_4$ plaquettes in the quasi-one dimensional chain cuprate Li$_2$CuO$_2$. By tuning the incoming photon energy to the O $K$-edge, we populate bound states related to the Zhang-Rice quasiparticles in the RIXS process. Both intra- and interchain Zhang-Rice singlets are observed and their occurrence is shown to depend on the nearest-neighbor spin-spin correlations, which are readily probed in this experiment. We also extract the binding energy of the Zhang-Rice singlet and identify the Zhang-Rice triplet excitation in the RIXS spectra., Comment: 8 pages, 4 figures, accepted for publication in Physical Review B

Two new ternary borides $TM$$_7$Fe$_3$B$_8$ ($TM$ = Nb, Ta) were synthesized by high-temperature thermal treatment of samples obtained by arc-melting. This new type of structure with space group $P$6/$mmm$, comprises $TM$ slabs containing isolated planar hexagonal [B$_6$] rings and iron centered $TM$ columns in a Kagome type of arrangement. Chemical bonding analysis in Nb$_7$Fe$_3$B$_8$ by means of the electron localizability approach reveals two-center interactions forming the Kagome net of Fe and embedded B, while weaker multicenter bonding present between this net and Nb atoms. Magnetic susceptibility measurements reveal antiferromagnetic order below $T_N$ = 240 K for Nb$_7$Fe$_3$B$_8$ and $T_N$ =265 K for Ta$_7$Fe$_3$B$_8$. Small remnant magnetization below 0.01 $\mu_B$/f.u. is observed in the antiferromagnetic state. The bulk nature of the magnetic transitions was confirmed by the hyperfine splitting of the M\"o{\ss}bauer spectra, the sizable anomalies in the specific heat capacity, and the kinks in the resistivity curves. The high-field paramagnetic susceptibilities fitted by the Curie-Weiss law show effective paramagnetic moments $\mu_{eff}$ about 3.1 $\mu_B$/Fe in both compounds. The temperature dependence of the electrical resistivity also reveals metallic character of both compounds. Density functional calculations corroborate the metallic behaviour of both compounds and demonstrate the formation of a sizable local magnetic moment on the Fe-sites. They indicate the presence of both antiferro- and ferromagnetic interactions., Comment: 11 pages, 11 figures

We report a combined experimental and theoretical study of the dependence of the superconductivity of the unconventional superconductor Sr$_2$RuO$_4$ on anisotropic strain. Novel piezoelectric apparatus is used to apply uniaxial pressures of up to $\sim$1~GPa along a $\langle 100 \rangle$ direction ($a$-axis) of the crystal lattice. $T_c$ increases from 1.5~K in unstrained material to 3.4~K at compression by $\approx$0.6\%, then falls steeply. The $c$-axis upper critical field for the strained $T_c$ = 3.4~K material is a factor of twenty larger than that of the unstrained crystal, whereas the in-plane ($a$-axis) critical field increases by only a factor of three. First-principles electronic structure calculations give evidence that the observed maximum $T_c$ occurs at or near a Lifshitz transition when the Fermi level passes through a van Hove singularity. Finally, we perform order parameter analyses using three-band renormalization group calculations. These, combined with the unexpectedly low in-plane critical field, open the possibility that the highly strained $T_c$=3.4~K Sr$_2$RuO$_4$ has an even- rather than an odd-parity order parameter. Potential implications such as a transition at nonzero strain between odd- and even-parity order parameters are discussed.

Magnetic and crystallographic properties of the mineral langite Cu$_4$(OH)$_6$SO$_4\cdot 2$H$_2$O are reported. Its layered crystal structure features a peculiar spatial arrangement of spin-$\frac12$ Cu$^{2+}$ ions that arises from a combination of corner- and edge-sharing chains. Experimentally, langite orders antiferromagnetically at $T_N\simeq 5.7$ K as revealed by magnetization and specific heat measurements. Despite this very low energy scale of the magnetic transition, langite features significantly stronger couplings on the order of 50-70 K. Half of the Cu$^{2+}$ spins are weakly coupled and saturate around 12T, where the magnetization reaches 0.5$\mu_B$/Cu. These findings are rationalized by density-functional band-structure calculations suggesting a complex interplay of frustrated exchange couplings in the magnetic planes. A simplified model of coupled magnetic sublattices explains the experimental features qualitatively. To start from reliable structural data, the crystal structure of langite in the 100-280 K temperature range has been determined by single-crystal x-ray diffraction, and the hydrogen positions were refined computationally.

The thermoelectric properties of single- and polycrystalline FeGa3 are systematically investigated over a wide temperature range. At low temperatures, below 20 K, previously not known pronounced peaks in the thermal conductivity (400-800 W K^-1m-1) with corresponding maxima in the thermopower (in the order of -16000 microV/K) were found in single crystalline samples. Measurements in single crystals along [100] and [001] directions indicate only a slight anisotropy in both the electrical and thermal transport. From susceptibility and heat capacity measurements, a structural or magnetic phase transition was excluded. Using density functional theory-based calculations, we have revisited the electronic structure of FeGa3 and compared the magnetic (including correlations) and non-magnetic electronic density of states. Thermopower at fixed carrier concentrations are calculated using semi-classical Boltzmann transport theory, and the calculated results match fairly with our experimental data and exclude the possibility of strong electronic correlations as an explanation for the low temperature enhancement. Eventually, after a careful review, we assign the peaks in the thermopower as a manifestation of the phonon-drag effect, which is supported by thermopower measurements in a magnetic field., Comment: Phys. Rev. B accepted (2014)

We present a detailed investigation of the electronic phase diagram of effectively charge compensated Ba1-xKx(Fe1-yCoy)2As2 with x/2 = y. Our experimental study by means of x-ray diffraction, M\"ossbauer spectroscopy, muon spin relaxation and ac susceptibility measurements on polycrystalline samples is complemented by density functional electronic structure calculations. For low substitution levels of x/2 = y \< 0.13, the system displays an orthorhombically distorted and antiferromagnetically ordered ground state. The low temperature structural and magnetic order parameters are successively reduced with increasing substitution level. We observe a linear relationship between the structural and the magnetic order parameter as a function of temperature and substitution level for x/2 = y \< 0.13. At intermediate substitution levels in the range between 0.13 and 0.19, we find superconductivity with a maximum Tc of 15 K coexisting with static magnetic order on a microscopic length scale. For higher substitution levels x/2 = y \> 0.25 a tetragonal non-magnetic ground state is observed. Our DFT calculations yield a signifcant reduction of the Fe 3d density of states at the Fermi energy and a strong suppression of the ordered magnetic moment in excellent agreement with experimental results. The appearance of superconductivity within the antiferromagnetic state can by explained by the introduction of disorder due to non-magnetic impurities to a system with a constant charge carrier density. Our experimental study by means of x-ray diffraction, M\"ossbauer spectroscopy, muon spin relaxation and ac susceptibility measurements on polycrystalline samples is complemented by density functional electronic structure calculations., Comment: 16 pages, 14 figures

A combined theoretical and experimental study of the natural Cu(2+)-mineral callaghanite is presented. Its crystal structure features well separated Cu$_2$(OH)$_6$ structural dimers with weakly bonded carbonate groups and water molecules in between. Susceptibility, field-dependent magnetization and specific heat measurements reveal a compound with a small spin gap of about 7 K. The observed magnetic properties are well described by a model of isolated antiferromagnetic spin dimers. Possible ferromagnetic interactions between the dimers amount to -1.5 K, at most. Different flavors of electronic structure calculations have been employed to locate the magnetic dimers in the crystal structure, i.e., to determine whether they coincide with the structural dimers or not. Calculations of the coupling between the structural dimers clearly show that magnetic and structural dimers are the same. For the intradimer coupling, however, the computational results confirmed a coupling strength close to zero but the sign of the coupling could not be determined unambiguously. Based on this finding, we then discuss how the reliability of the numerical methods depends on the characteristics of exchange pathways and on structural features of the compound in general. Eventually, we try to provide a minimum coupling strength that is needed for a reliable computational description.

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 report on the quasi-two-dimensional magnetism of the natural mineral diaboleite Pb2Cu(OH)4Cl2 with a tetragonal crystal structure, which is closely related to that of the frustrated spin-1/2 magnet PbVO3. Magnetic susceptibility of diaboleite is well described by a Heisenberg spin model on a diluted square lattice with the nearest-neighbor exchange of J~35 K and about 5% of non-magnetic impurities. The dilution of the spin lattice reflects the formation of Cu vacancies that are tolerated by the crystal structure of diaboleite. The weak coupling between the magnetic planes triggers the long-range antiferromagnetic order below TN~11 K. No evidence of magnetic frustration is found. We also analyze the signatures of the long-range order in heat-capacity data, and discuss the capability of identifying magnetic transitions with heat-capacity measurements., Comment: 10 pages, 10 figures + Supplementary Information

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 J4, as well as a large number of nonequivalent interdimer couplings quantified by an effective exchange parameter Jeff. In (CuCl)LaTa2O7, the interdimer couplings are sufficiently strong to induce the long-range magnetic order with the Neel temperature TN~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 Jeff/J4~1.6 and J4~16 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 Jeff/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., Comment: 13 pages, 13 figures, 4 tables + Supplementary information

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

We report a comprehensive experimental and theoretical study of the quasi-one-dimensional quantum magnet CuNCN. Based on magnetization measurements above room temperature as well as muon spin rotation and electron spin resonance measurements, we unequivocally establish the localized Cu+2-based magnetism and the magnetic transition around 70 K, both controversially discussed in the previous literature. Thermodynamic data conform to the uniform-spin-chain model with a nearest-neighbor intrachain coupling of about 2300 K, in remarkable agreement with the microscopic magnetic model based on density functional theory band-structure calculations. Using exact diagonalization and the coupled-cluster method, we derive a collinear antiferromagnetic order with a strongly reduced ordered moment of about 0.4 mu_B, indicating strong quantum fluctuations inherent to this quasi-one-dimensional spin system. We re-analyze the available neutron-scattering data, and conclude that they are not sufficient to resolve or disprove the magnetic order in CuNCN. By contrast, spectroscopic techniques indeed show signatures of long-range magnetic order below 70 K, yet with a rather broad distribution of internal field probed by implanted muons. We contemplate the possible structural origin of this effect and emphasize peculiar features of the microstructure studied with synchrotron powder x-ray diffraction., Comment: 17 pages, 17 figures, 1 table

In a recent Letter [PRL, 107, 047208 (2011)], Zorko et al. report on an "unexpected inhomogeneous magnetism" related to "a peculiar fragility" of the resonating-valence-bond (RVB) electronic state in the spin-1/2 quantum magnet CuNCN. Here, we show that: i) the spin model of the anisotropic triangular lattice (ATL), as proposed by Zorko et al., does not apply to CuNCN; ii) this model does not support the proclaimed RVB ground state in the relevant parameter range; iii) the magnetic state of CuNCN is not necessarily inhomogeneous., Comment: one-page Comment + additional information

Thermoelectric effects enable the direct conversion between thermal and electrical energy and provide an alternative route for power generation and refrigeration. The clathrate Ba8Ga16Ge30 has the highest figure of merit (ZT ~ 1) among other members in the family of type-I inorganic clathrates. Enhancement of the thermoelectric properties have been observed in multilayered superlattices, quantum wires and in nanostructured materials, either due to the increase in power-factor (S^{2}\sigma) or due to the reduction of lattice thermal conductivity (\kappa). Here, we investigate the thermoelectric properties of two-dimensional slabs with varying thickness of Ba8Ga16Ge30 using semi-classical Boltzmann transport theory with constant scattering approximation. We observe that, there exists a delicate balance between the electrical conductivity and the electronic part of the thermal conductivity in reduced dimensions and the insights from these results can directly be used to control particle size in nanostructuring experiments. The calculated properties are consistent with the recent, first measurements on bulk nanostructured samples.

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

Recently, we reported [M. Wagner et al., J. Mater. Res. 26, 1886 (2011)] transport measurements on the semiconducting intermetallic system RuIn3 and its substitution derivatives RuIn_{3-x}A_{x} (A = Sn, Zn). Higher values of the thermoelectric figure of merit (zT = 0.45) compared to the parent compound were achieved by chemical substitution. Here, using density functional theory based calculations, we report on the microscopic picture behind the measured phenomenon. We show in detail that the electronic structure of the substitution variants of the intermetallic system RuIn_{3-x}A_{x} (A = Sn, Zn) changes in a rigid-band like fashion. This behavior makes possible the fine tuning of the substitution concentration to take advantage of the sharp peak-like features in the density of states of the semiconducting parent compound. Trends in the transport properties calculated using the semi-classical Boltzmann transport equations within the constant scattering time approximation are in good agreement with the former experimental results for RuIn_{3-x}Sn_{x}. Based on the calculated thermopower for the p-doped systems, we reinvestigated the Zn-substituted derivative and obtained ZnO-free RuIn_{3-x}Zn_{x}. The new experimental results are consistent with the calculated trend in thermopower and yield large zT value of 0.8., Comment: PRB Accepted, 11 pages, 10 figures

Based on density functional calculations, we report on the orbital order and microscopic magnetic model of FeNCN, a prototype compound for orbital-only models. Despite having a similar energy scale, the spin and orbital degrees of freedom in FeNCN are only weakly coupled. The ground-state configuration features the doubly occupied d_{3z^2-r^2} (a1g) orbital and four singly-occupied d orbitals resulting in the spin S=2 on the Fe+2 atoms, whereas alternative (Eg') configurations are about 75 meV/f.u. higher in energy. Calculated exchange couplings and band gap are in good agreement with the available experimental data. Experimental effects arising from possible orbital excitations are discussed., Comment: 4 pages + supplementary information

For the 1D-frustrated ferromagnetic J_1-J_2 model with interchain coupling added, we analyze the dynamical and static structure factor S(k,omega), the pitch angle phi of the magnetic structure, the magnetization curve of edge-shared chain cuprates, and focus on LiCuVO4 for which neither a perturbed spinon nor a spin wave approach can be applied. phi is found to be most sensitive to the interplay of frustration and quantum fluctuations. For LiVCuO4 the obtained exchange parameters J are in accord with the results for a realistic 5-band extended Hubbard model and LSDA + U predictions yielding alpha=J_2/|J_1| about 0.75 in contrast to 5.5 > alpha > 1.42 suggested in the literature. The alpha-regime of the empirical phi-values in NaCu2O2 and linarite are considered, too., Comment: 7 pages, 7 figures, (1 figure added), improved text including also the abstract (the present second version has been submitted to EPL 26.10.2011, so far with one missing first referee report)

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., Comment: 10 pages, 7 figures

A microscopic magnetic model of the low-pressure modification of CdVO3 is established, based on density functional theory (DFT) band-structure calculations, magnetization measurements, and quantum Monte-Carlo simulations. This compound is a rare example of a quasi-one-dimensional spin-1/2 system showing exclusively ferromagnetic exchange. The spin lattice of CdVO3 entails zigzag chains with an effective intrachain coupling J ~ -90 K and interchain couplings of Jc ~ -18 K and Ja ~ -3 K. Quantum fluctuations are partially suppressed by the sizable interchain coupling Jc that leads to an intermediate regime between one-dimensional and two-dimensional ferromagnetic systems. Apart from the peculiar spin model, CdVO3 features an unusual mechanism of ferromagnetic superexchange. The couplings largely originate from Cd 5s states mediating hoppings between half-filled and empty 3d states of V+4., Comment: 11 pages, 9 figures, 5 tables. Published version with an additional explanation of methodological issues

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 on the crystal structure and magnetic behavior of the spin-1/2 compound AgVOAsO4. Magnetic susceptibility, high-field magnetization, and electron spin resonance measurements identify AgVOAsO4 as a gapped quantum magnet with a spin gap Delta ~ 13 K and a saturation field H_s ~ 48.5 T. Extensive band structure calculations establish the microscopic magnetic model of spin chains with alternating exchange couplings J ~ 40 K and J' ~ 26 K. However, the precise evaluation of the spin gap emphasizes the role of interchain couplings which are frustrated due to the peculiar crystal structure of the compound. The unusual spin model and the low energy scale of the exchange couplings make AgVOAsO4 a promising candidate for an experimental investigation of Bose-Einstein condensation and other exotic ground states in high magnetic fields., Comment: 10 pages + supplementary information and cif files, 7 figures, 6 tables

The natural mineral azurite Cu$_3$(CO$_3$)$_2$(OH)$_2$ is a frustrated magnet displaying unusual and controversially discussed magnetic behavior. Motivated by the lack of a unified description for this system, we perform a theoretical study based on density functional theory as well as state-of-the-art numerical many-body calculations. We propose an effective generalized spin-1/2 diamond chain model which provides a consistent description of experiments: low-temperature magnetization, inelastic neutron scattering, nuclear magnetic resonance measurements, magnetic susceptibility as well as new specific heat measurements. With this study we demonstrate that the balanced combination of first principles with powerful many-body methods successfully describes the behavior of this frustrated material., Comment: final version to appear in Phys. Rev. Lett.; 10 pages, 9 figures, 4 tables (including supplementary material)

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., Comment: Extended version: 9 pages, 7 figures, 4 tables

We report a systematic study on the influence of antiferromagnetic and ferromagnetic phases of Eu^2+ moments on the superconducting phase upon doping the As site by isovalent P, which acts as chemical pressure on EuFe_2As_2. Bulk superconductivity with transition temperatures of 22 K and 28 K are observed for x=0.16 and 0.20 samples respectively. The Eu ions order antiferromagnetically for x<=0.13, while a crossover is observed for x>=0.22 whereupon the Eu ions order ferromagnetically. Density functional theory based calculations reproduce the observed experimental findings consistently. We discuss in detail the coexistence of superconductivity and magnetism in a tiny region of the phase space and comment on the competition of ferromagnetism and superconductivity in the title compound., Comment: 6 pages, 5 figures, 1 table

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., Comment: 6 pages, 6 figures, 1 table

We apply density functional theory band structure calculations, the coupled-cluster method, and exact diagonalization to investigate the microscopic magnetic model of the spin-1/2 compound Cu2GeO4. The model is quasi-two-dimensional, with uniform spin chains along one direction and frustrated spin chains along the other direction. The coupling along the uniform chains is antiferromagnetic, J 130 K. The couplings along the frustrated chains are J1 -60 K and J2 80 K between nearest neighbors and next-nearest neighbors, respectively. The ground state of the quantum model is a spiral, with the reduced sublattice magnetization of 0.62 mu_B and the pitch angle of 84 deg, both renormalized by quantum effects. The proposed spiral ground state of Cu2GeO4 opens a way to magnetoelectric effects in this compound., Comment: Extended version: 8 pages, 5 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.