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Chemical doping of known superconductors is a probate strategy to test and enhance our understanding of which parameters control the critical temperature T-c and the critical magnetic fields. The transition metal chalcogenide PdTe is considered a conventional type II superconductor but its resilience to magnetic Fe doping is noteworthy. Isoelectronic Ni doping has been performed, but the effects of doping charges into PdTe have been so far unexplored. We follow two strategies to introduce holes into PdTe and to exert chemical pressure on it: by pnictogen doping on the chalcogen site PdTe1-xSbx and by systematically introducing a Pd deficiency in Pd1-yTe. We find that the superconducting T-c is very sensitive to both kinds of doping. We employ density functional theory to rationalize the observations. We conclude that in PdTe, the effects of charge doping take the lead but we can also identify a structural parameter that correlates with T-c.

A family of titanium oxypnictide materials BaTi2Pn2O (Pn = pnictogen) becomes superconducting when a charge and/or spin density wave is suppressed. With hole doping, isovalent doping and pressure, a whole range of tuning parameters is available. We investigate how charge doping controls the superconducting transition temperature Tc. To this end, we use experimental crystal structure data to determine the electronic structure and Fermi surface evolution along the doping path. We show that a naive approach to calculating Tc via the density of states at the Fermi level and the McMillan formula systematically fails to yield the observed Tc variation. On the other hand, spin fluctuation theory pairing calculations allow us to consistently explain the Tc increase with doping. All alkali doped materials Ba1-xAxTi2Sb2O (A = Na, K, Rb) are described by a sign-changing s-wave order parameter. Susceptibilities also reveal that the physics of the materials is controlled by a single Ti 3d orbital., 9 pages, 12 figures

The Ti$_2$Ni and the related $\eta$-carbide structure are known to exhibit various intriguing physical properties. The Ti$_2$Ni structure with the cubic space group $Fd\bar{3}m$ is surprisingly complex, consisting of a unit cell with 96 metal atoms. The related $\eta$-carbide compounds correspond to a filled version of the Ti$_2$Ni structure. Here, we report on the structure and superconductivity in the $\eta$-carbide type suboxides Ti$_4$M$_2$O with M = Co, Rh, Ir. We have successfully synthesized all three compounds in single phase form. We find all three compounds to be type-II bulk superconductors with transition temperatures of $T_{\rm c}$ = 2.7, 2.8, and 5.4 K, and with normalized specific heat jumps of $\Delta C/\gamma T_{\rm c}$ = 1.65, 1.28, and 1.80 for Ti$_4$Co$_2$O, Ti$_4$Rh$_2$O, and Ti$_4$Ir$_2$O, respectively. We find that all three superconductors, exhibit high upper-critical fields. Particularly noteworthy is Ti$_4$Ir$_2$O with an upper critical field of $\mu_0 H_{\rm c2}{\rm (0)}$ =~16.06~T, which exceeds by far the weak-coupling Pauli limit of 9.86~T. The role of the void filling light atom X has so far been uncertain for the overall physical properties of these materials. Herein, we have successfully grown single crystals of Ti$_2$Co. In contrast to the metallic $\eta$-carbide type suboxides Ti$_4$M$_2$O, we find that Ti$_2$Co displays a semimetallic behavior. Hence, the octahedral void-filling oxygen plays a crucial role for the overall physical properties, even though its effect on the crystal structure is small. Our results indicate that the design of new superconductors by incorporation of electron-acceptor atoms may in the Ti$_2$Ni-type structures and other materials with crystallographic void position be a promising future approach. The remarkably high upper critical fields, in this family of compounds, may furthermore spark significant future interest., Comment: Submitted: 3. August 2021, published: 1. November 2021, Supporting Information at publisher's page: https://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.1c02683/suppl_file/cm1c02683_si_001.pdf

Henmilite {${\mathrm{Ca}}_{2}\mathrm{Cu}{(\mathrm{OH})}_{4}{[\mathrm{B}{(\mathrm{OH})}_{4}]}_{2}$} is a blue calcium copper borate mineral found only in the Fuka mine, Okayama Prefecture, Japan. Crystal structure refinement, magnetic and specific heat measurements, and density functional theory (DFT) calculations are performed to clarify its magnetic properties. Synchrotron x-ray diffraction experiments reveal that the hydrogen-bonded chains are arranged in an antiferroelectric manner, doubling the unit cell along the $a$ axis. An antiferromagnetic transition is observed at 0.2 K at zero magnetic field. Furthermore, a dome-shaped antiferromagnetic ordering region exists in the temperature--magnetic-field phase diagram, indicating the presence of quantum spin fluctuations. The obtained crystal structure in combination with DFT calculations suggests that the system has a coupled two-leg ladder magnetic lattice, explaining the very low ordering temperature.

Quantum spin liquids are exotic states of matter that form when strongly frustrated magnetic interactions induce a highly entangled quantum paramagnet far below the energy scale of the magnetic interactions. Three-dimensional cases are especially challenging due to the significant reduction of the influence of quantum fluctuations. Here, we report the magnetic characterization of ${\mathrm{K}}_{2}{\mathrm{Ni}}_{2}({\mathrm{SO}}_{4}{)}_{3}$ forming a three-dimensional network of ${\mathrm{Ni}}^{2+}$ spins. Using density functional theory calculations, we show that this network consists of two interconnected spin-1 trillium lattices. In the absence of a magnetic field, magnetization, specific heat, neutron scattering, and muon spin relaxation experiments demonstrate a highly correlated and dynamic state, coexisting with a peculiar, very small static component exhibiting a strongly renormalized moment. A magnetic field $B\ensuremath{\gtrsim}4\text{ }\text{ }\mathrm{T}$ diminishes the ordered component and drives the system into a pure quantum spin liquid state. This shows that a system of interconnected $S=1$ trillium lattices exhibits a significantly elevated level of geometrical frustration.

Organic salts represent an ideal experimental playground for studying the interplay between magnetic and charge degrees of freedom, which has culminated in the discovery of several spin-liquid candidates such as $\ensuremath{\kappa}\text{\ensuremath{-}}(\mathrm{ET}{)}_{2}{\mathrm{Cu}}_{2}(\mathrm{CN}{)}_{3}$ ($\ensuremath{\kappa}\text{\ensuremath{-}}\mathrm{Cu}$). Recent theoretical studies indicate the possibility of chiral spin liquids stabilized by ring exchange, but the parent states with chiral magnetic order have not been observed in this material family. In this Letter, we discuss the properties of the recently synthesized $\ensuremath{\kappa}\text{\ensuremath{-}}(\mathrm{BETS}{)}_{2}\mathrm{Mn}[\mathrm{N}(\mathrm{CN}{)}_{2}{]}_{3}$ ($\ensuremath{\kappa}\text{\ensuremath{-}}\mathrm{Mn}$). Based on analysis of specific heat, magnetic torque, and NMR measurements combined with ab initio calculations, we identify a spin-vortex crystal order. These observations definitively confirm the importance of ring exchange in these materials and support the proposed chiral spin-liquid scenario for triangular lattice organics.

We present a combined experimental and theoretical study of the mineral atacamite ${\mathrm{Cu}}_{2}\mathrm{Cl}(\mathrm{OH}{)}_{3}$. Density-functional theory yields a Hamiltonian describing anisotropic sawtooth chains with weak 3D connections. Experimentally, we fully characterize the antiferromagnetically ordered state. Magnetic order shows a complex evolution with the magnetic field, while, starting at 31.5 T, we observe a plateaulike magnetization at about ${M}_{\mathrm{sat}}/2$. Based on complementary theoretical approaches, we show that the latter is unrelated to the known magnetization plateau of a sawtooth chain. Instead, we provide evidence that the magnetization process in atacamite is a field-driven canting of a 3D network of weakly coupled sawtooth chains that form giant moments.

Ferrotoroidal order, which represents a spontaneous arrangement of toroidal moments, has recently been found in a few linear magnetoelectric materials. However, tuning toroidal moments in these materials is challenging. Here, we report switching between ferritoroidal and ferrotoroidal phases by a small magnetic field, in a chiral triangular-lattice magnet BaCoSiO4 with tri-spin vortices. Upon applying a magnetic field, we observe multi-stair metamagnetic transitions, characterized by equidistant steps in the net magnetic and toroidal moments. This highly unusual ferri-ferroic order appears to come as a result of an unusual hierarchy of frustrated isotropic exchange couplings revealed by first principle calculations, and the antisymmetric exchange interactions driven by the structural chirality. In contrast to the previously known toroidal materials identified via a linear magnetoelectric effect, BaCoSiO4 is a qualitatively new multiferroic with an unusual coupling between several different orders, and opens up new avenues for realizing easily tunable toroidal orders. Toroidal moments arise from vortex like spin arrangements. These moments can then interact, giving rise to ferri- or ferro-toroidal order, though controlling such order is difficult. Here, the authors demonstrate a ferri-toroidal state in BaCoSiO4, which under an applied magnetic field exhibits multiple toroidal and metamagnetic transitions.

The pressure-induced change in the electronic structures of the superconductors ${\mathrm{Bi}}_{2}{\mathrm{Se}}_{3}$ and ${\mathrm{Ag}}_{x}{\mathrm{Bi}}_{2}{\mathrm{Se}}_{3}$ has been measured with high-resolution x-ray absorption spectroscopy. As a common feature for these compounds, we find that pressure causes the broadening of the Se $4p$ band and an energy shift of the Bi $6s$ band above the Fermi level up to the pressure of the first structural transition. These results, corroborated by density functional theory calculations, correlate with an increase of the carrier density, the disappearance of the band gap, and the emergence of superconductivity. The electronic structure changes significantly at the pressure of the first structural transition, which may be a trigger of the emergence of superconductivity, while above the pressure of the first phase transition it does not change much even around the second phase transition pressure, corresponding to the nearly constant ${T}_{\mathrm{c}}$ above the pressure of the second structural transition.

In conventional quasi-one-dimensional antiferromagnets with quantum spins, magnetic excitations are carried by either magnons or spinons in different energy regimes: they do not coexist independently, nor could they interact with each other. In this Letter, by combining inelastic neutron scattering, quantum Monte Carlo simulations and Random Phase Approximation calculations, we report the discovery and discuss the physics of the coexistence of magnons and spinons and their interactions in Botallackite-Cu2(OH)3Br. This is a unique quantum antiferromagnet consisting of alternating ferromagnetic and antiferromagnetic Spin-1/2 chains with weak inter-chain couplings. Our study presents a new paradigm where one can study the interaction between two different types of magnetic quasiparticles, magnons and spinons., Comment: Accepted by PRL

Crystal and magnetic structures of the mineral centennialite ${\mathrm{CaCu}}_{3}{(\mathrm{OH})}_{6}{\mathrm{Cl}}_{2}\ifmmode\cdot\else\textperiodcentered\fi{}0.6{\mathrm{H}}_{2}\mathrm{O}$ are investigated by means of synchrotron x-ray diffraction and neutron diffraction measurements complemented by density functional theory (DFT) and pseudofermion functional renormalization group (PFFRG) calculations. ${\mathrm{CaCu}}_{3}{(\mathrm{OH})}_{6}{\mathrm{Cl}}_{2}\ifmmode\cdot\else\textperiodcentered\fi{}0.6{\mathrm{H}}_{2}\mathrm{O}$ crystallizes in the $P\overline{3}m1$ space group and ${\mathrm{Cu}}^{2+}$ ions form a geometrically perfect kagome network with antiferromagnetic ${J}_{1}$. No intersite disorder between ${\mathrm{Cu}}^{2+}$ and ${\mathrm{Ca}}^{2+}$ ions is detected. ${\mathrm{CaCu}}_{3}{(\mathrm{OH})}_{6}{\mathrm{Cl}}_{2}\ifmmode\cdot\else\textperiodcentered\fi{}0.6{\mathrm{H}}_{2}\mathrm{O}$ enters a magnetic long-range ordered state below ${T}_{\text{N}}=7.2$ K, and the $\mathbf{q}=\mathbf{0}$ magnetic structure with negative vector spin chirality is obtained. The ordered moment at 0.3 K is suppressed to $0.58(2){\ensuremath{\mu}}_{\text{B}}$. Our DFT calculations indicate the presence of antiferromagnetic ${J}_{2}$ and ferromagnetic ${J}_{d}$ superexchange couplings of a strength which places the system at the crossroads of three magnetic orders (at the classical level) and a spin-$\frac{1}{2}$ PFFRG analysis shows a dominance of $\mathbf{q}=\mathbf{0}$ type magnetic correlations, consistent with and indicating proximity to the observed $\mathbf{q}=\mathbf{0}$ spin structure. The results suggest that this material is located close to a quantum critical point and is a good realization of a ${J}_{1}\ensuremath{-}{J}_{2}\ensuremath{-}{J}_{d}$ kagome antiferromagnet.

The van-der-Waals gap of iron chalcogenide superconductors can be intercalated with a variety of inorganic and organic compounds that modify the electron doping level of the iron layers. In Lix(C3N2H10)0.37FeSe, a dome in the superconducting transition temperature Tc has been reported to occur in the doping range of x=0.06 to x=0.68. We use a combination of density functional theory and spin fluctuation theory to capture the evolution of superconducting transition temperatures theoretically. We clearly demonstrate how the changing electronic structure supports an increasing superconducting Tc. The suppression of Tc at high doping levels can, however, only be understood by analyzing the magnetic tendencies, which evolve from stripe-type at low doping to bicollinear at high doping., 7 pages, 5 figures, supplement

${\mathrm{AgSnSe}}_{2}$, by formal electron count, should have Sn in a highly unusual $3+$ valence state and was therefore suggested to be a valence-skipping compound with potential for negative-$U$ centers and local electron pairing. It has been proposed that the latter may be the mechanism beyond seemingly conventional superconductivity in this compound. We report NMR measurements and first-principles calculations that agree with each other perfectly, and both indicate that valence skipping does not take place and the highly unusual ${\mathrm{Sn}}^{3+}$ state is realized instead, likely because of geometrical constraint prohibiting a breathing distortion that could screen the on-site Coulomb repulsion.

We present single-crystal x-ray diffraction measurements, optical investigations, and electronic structure calculations for the organic charge-transfer salt ${\ensuremath{\beta}}^{\ensuremath{'}}$-(BEDT-TTF)${}_{2}{\mathrm{CF}}_{3}{\mathrm{CF}}_{2}{\mathrm{SO}}_{3}$ synthesized by electrocrystallization. Electronic structure calculations confirm the quasi-one-dimensional behavior of the compound and optical conductivity measurements reveal the dimer-Mott insulating nature of the system. The splitting of the charge-sensitive ${\ensuremath{\nu}}_{2}$ mode in Raman spectra demonstrates the onset of an interlayer charge-ordered phase below 25 K, also suggested by the crystal structure considerations. This transition is accompanied by clear signatures of a lattice distortion in the BEDT-TTF donor layer, as shown by a splitting of the vibrational ${\ensuremath{\nu}}_{3}$ mode in infrared spectra. At the same time, the sharp redshift of the ${\ensuremath{\nu}}_{1}$ mode involving the BEDT-TTF ethylene groups strongly suggests a significant modification of the hydrogen-type bonding present between the BEDT-TTF donor layer and the ${\mathrm{CF}}_{3}{\mathrm{CF}}_{2}{\mathrm{SO}}_{3}^{\ensuremath{-}}$ anion layer. These observations point to a subtle interplay of charge and lattice degrees of freedom at the phase transition.

We report an efficient algorithm for calculating momentum-space integrals in solid state systems on modern graphics processing units (GPUs). Our algorithm is based on the tetrahedron method, which we demonstrate to be ideally suited for execution in a GPU framework. In order to achieve maximum performance, all floating point operations are executed in single precision. For benchmarking our implementation within the CUDA programming framework we calculate the orbital-resolved density of states in an iron-based superconductor. However, our algorithm is general enough for the achieved improvements to carry over to the calculation of other momentum integrals such as, e.g. susceptibilities. If our program code is integrated into an existing program for the central processing unit (CPU), i.e. when data transfer overheads exist, speedups of up to a factor ∼ 130 compared to a pure CPU implementation can be achieved, largely depending on the problem size. In case our program code is integrated into an existing GPU program, speedups over a CPU implementation of up to a factor ∼ 165 are possible, even for moderately sized workloads.

The recently discovered Fe-based superconductor (FeBS) ${\mathrm{LaFe}}_{2}{\mathrm{As}}_{2}$ seems to break away from an established pattern that doping an FeBS beyond $0.2e/\mathrm{Fe}$ destroys superconductivity. ${\mathrm{LaFe}}_{2}{\mathrm{As}}_{2}$ has an apparent doping of $0.5e$, yet superconducts at 12.1 K. Its Fermi surface bears no visual resemblance with the canonical FeBS fermiology. It also exhibits two phases, none magnetic and only one superconducting. We show that the difference between them nonetheless has a magnetic origin, the one featuring disordered moments, and the other locally nonmagnetic. We find that La there assumes an unusual valence of $+2.6$ to $+2.7$, so that the effective doping is reduced to $0.30\ensuremath{-}0.35e$. A closer look reveals the same key elements: hole Fermi surfaces near $\mathrm{\ensuremath{\Gamma}}\ensuremath{-}Z$ and electron ones near the $X\ensuremath{-}P$ lines, with the corresponding peak in susceptibility, and a strong tendency to stripe magnetism. The physics of ${\mathrm{LaFe}}_{2}{\mathrm{As}}_{2}$ is thus more similar to the FeBS paradigm than hitherto appreciated.

We synthesized a kagome fluoride ${\mathrm{Cs}}_{2}{\mathrm{LiTi}}_{3}{\mathrm{F}}_{12}$ with $S=1/2$ spins, and studied magnetic properties of the compound. The temperature dependence of the magnetic susceptibility indicates that it has dominant antiferromagnetic interactions and that it has no magnetic order down to 2 K. We found two magnetization plateaus in its magnetization process approximately at 1/3 and 0.8 ${\ensuremath{\mu}}_{\mathrm{B}}$ per Ti. The monoclinic crystal structure gives four inequivalent nearest-neighbor exchange interactions. Our density functional theory calculations suggest that three of them are antiferromagnetic and one of them is weakly ferromagnetic, resulting in a magnetic system composed of antiferromagnetically coupled linear chains and $\mathrm{\ensuremath{\Delta}}$ chains. This explains the observed suppression of magnetic order. Numerical diagonalization gives a magnetization curve in good agreement with the experimental results.

The interaction of trimethyl(methylcyclopentadienyl)platinum(IV) ((C5H4CH3)Pt(CH3)3) molecules on fully and partially hydroxylated SiO2 surfaces, as well as the dynamics of this interaction were investigated using density functional theory (DFT) and finite temperature DFT-based molecular dynamics simulations. Fully and partially hydroxylated surfaces represent substrates before and after electron beam treatment and this study examines the role of electron beam pretreatment on the substrates in the initial stages of precursor dissociation and formation of Pt deposits. Our simulations show that on fully hydroxylated surfaces or untreated surfaces, the precursor molecules remain inactivated while we observe fragmentation of (C5H4CH3)Pt(CH3)3 on partially hydroxylated surfaces. The behavior of precursor molecules on the partially hydroxylated surfaces has been found to depend on the initial orientation of the molecule and the distribution of surface active sites. Based on the observations from the simulations and available experiments, we discuss possible dissociation channels of the precursor.

We systematically investigated the pressure dependence of electrical transport and the crystal structure of topological insulator, $\mathrm{B}{\mathrm{i}}_{2\ensuremath{-}x}\mathrm{S}{\mathrm{b}}_{x}\mathrm{T}{\mathrm{e}}_{3\ensuremath{-}y}\mathrm{S}{\mathrm{e}}_{y}$, which showed no superconductivity down to 2.0 K at ambient pressure. The $\mathrm{B}{\mathrm{i}}_{2\ensuremath{-}x}\mathrm{S}{\mathrm{b}}_{x}\mathrm{T}{\mathrm{e}}_{3\ensuremath{-}y}\mathrm{S}{\mathrm{e}}_{y}$ crystal showed two structural phase transitions under pressure, from rhombohedral structure (space group No. 166, $R\overline{3}m$, termed phase I) to monoclinic structure (space group No. 12, $C2/m$, termed phase II), and from phase II to another monoclinic structure (space group No. 12, $C2/m$, termed phase III). Superconductivity appeared when applying pressure; actually the superconductivity of all $\mathrm{B}{\mathrm{i}}_{2\ensuremath{-}x}\mathrm{S}{\mathrm{b}}_{x}\mathrm{T}{\mathrm{e}}_{3\ensuremath{-}y}\mathrm{S}{\mathrm{e}}_{y}$ samples emerged in phase I. The superconducting transition temperature, ${T}_{\mathrm{c}}$, increased against pressure in a pressure range of 0--15 GPa for all $\mathrm{B}{\mathrm{i}}_{2\ensuremath{-}x}\mathrm{S}{\mathrm{b}}_{x}\mathrm{T}{\mathrm{e}}_{3\ensuremath{-}y}\mathrm{S}{\mathrm{e}}_{y}$ samples, and the maximum ${T}_{\mathrm{c}}$ was 5.45 K, recorded at 13.5 GPa in $\mathrm{B}{\mathrm{i}}_{2\ensuremath{-}x}\mathrm{S}{\mathrm{b}}_{x}\mathrm{T}{\mathrm{e}}_{3\ensuremath{-}y}\mathrm{S}{\mathrm{e}}_{y}$ at $x=0$ and $y=1.0$. The magnetic field (H) dependence of the R--T plot for $\mathrm{B}{\mathrm{i}}_{2\ensuremath{-}x}\mathrm{S}{\mathrm{b}}_{x}\mathrm{T}{\mathrm{e}}_{3\ensuremath{-}y}\mathrm{S}{\mathrm{e}}_{y}$ was measured to characterize the superconducting pairing mechanism of pressure-induced superconducting phase.

The crystal structure and magnetic properties of the spin-1 triangular-lattice antiferromagnet ${\mathrm{Ba}}_{2}{\mathrm{La}}_{2}{\mathrm{NiTe}}_{2}{\mathrm{O}}_{12}$ are reported. Its crystal structure is trigonal $R\overline{3}$, which is the same as that of ${\mathrm{Ba}}_{2}{\mathrm{La}}_{2}{\mathrm{NiW}}_{2}{\mathrm{O}}_{12}$ [Y. Doi et al., J. Phys.: Condens. Matter 29, 365802 (2017)]. However, the exchange interaction $J/{k}_{\mathrm{B}}\ensuremath{\simeq}19$ K is much greater than that observed in the tungsten system. At zero magnetic field, ${\mathrm{Ba}}_{2}{\mathrm{La}}_{2}{\mathrm{NiTe}}_{2}{\mathrm{O}}_{12}$ undergoes successive magnetic phase transitions at ${T}_{\mathrm{N}1}=9.8$ K and ${T}_{\mathrm{N}2}=8.9$ K. The ground state is accompanied by a weak ferromagnetic moment. These results indicate that the ground-state spin structure is a triangular structure in a plane perpendicular to the triangular lattice owing to the small easy-axis-type anisotropy. The magnetization curve exhibits the one-third plateau characteristic of a two-dimensional triangular-lattice Heisenberg-like antiferromagnet. Exchange constants are also evaluated using density functional theory (DFT). The DFT results demonstrate the large difference in the exchange constants between tellurium and tungsten systems and the good two-dimensionality of the tellurium system.

We investigate the connection between highly frustrated kagome based Hamiltonians and a recently synthesized family of materials containing ${\mathrm{Ti}}^{3+}\phantom{\rule{4pt}{0ex}}S=\frac{1}{2}$ ions. Employing a combination of all electron density functional theory and numerical diagonalization techniques, we establish the Heisenberg Hamiltonians for the distorted kagome antiferromagnets ${\mathrm{Rb}}_{2}{\mathrm{NaTi}}_{3}{\mathrm{F}}_{12},{\mathrm{Cs}}_{2}{\mathrm{NaTi}}_{3}{\mathrm{F}}_{12}$, and ${\mathrm{Cs}}_{2}{\mathrm{KTi}}_{3}{\mathrm{F}}_{12}$. We determine magnetization curves in excellent agreement with experimental observations. Our calculations successfully clarify the relationship between the experimental observations and the magnetization-plateau behavior at $\frac{1}{3}$ height of the saturation and predict characteristic behaviors under fields that are higher than the experimentally measured region. We demonstrate that the studied Ti(III) family of materials interpolates between the kagome strip and kagome lattice.

Neutron scattering experiments reveal evidence of magnetic frustration as electrons gridlock in chromium-doped V${}_{2}$O${}_{3}$.

We address the long-standing problem of the microscopic origin of the richly diverse phenomena in the chromium breathing pyrochlore material family. Combining electronic structure and renormalization group techniques we resolve the magnetic interactions and analyze their reciprocal-space susceptibility. We show that the physics of these materials is principally governed by long-range Heisenberg Hamiltonian interactions, a hitherto unappreciated fact. Our calculations uncover that in these isostructural compounds, the choice of chalcogen triggers a proximity of the materials to classical spin liquids featuring degenerate manifolds of wave-vectors of different dimensions: A Coulomb phase with three-dimensional degeneracy for LiInCr4O8 and LiGaCr4O8, a spiral spin liquid with two-dimensional degeneracy for CuInCr4Se8 and one-dimensional line degeneracies characteristic of the face-centered cubic antiferromagnet for LiInCr4S8, LiGaCr4S8 and CuInCr4S8. The surprisingly complex array of prototypical pyrochlore behaviors we discovered in chromium spinels may inspire studies of transition paths between different semi-classical spin liquids by doping or pressure., Comment: 14 pages, 5 figures, 1 table, supplement

We investigate the quantum Heisenberg model on the pyrochlore lattice for a generic spin $S$ in the presence of nearest-neighbor $J_{1}$ and second-nearest-neighbor $J_{2}$ exchange interactions. By employing the pseudofermion functional renormalization group method, we find, for $S=1/2$ and $S=1$, an extended quantum-spin-liquid phase centered around $J_{2}=0$, which is shown to be robust against the introduction of breathing anisotropy. The effects of temperature, quantum fluctuations, breathing anisotropies, and a $J_{2}$ coupling on the nature of the scattering profile, and the pinch points, in particular, are studied. For the magnetic phases of the $J_{1}$-$J_{2}$ model, quantum fluctuations are shown to renormalize phase boundaries compared to the classical model and to modify the ordering wave vectors of spiral magnetic states, while no new magnetic orders are stabilized., Comment: Published version. 34 pages, 25 figures, 2 tables

We report on high-pressure $p \leq 45$ GPa resistivity measurements on the perovskite-related mixed-valent compound CsAuBr$_3$. The compounds high-pressure resistivity can be classified into three regions: For low pressures ($p < 10$ GPa) an insulator to metal transition is observed; between $p= 10$ GPa and 14 GPa the room temperature resistivity goes through a minimum and increases again; above $p = 14$ GPa a semiconducting state is observed. From this pressure up to the highest pressure of $p = 45$ GPa reached in this experiment, the room-temperature resistivity remains nearly constant. We find an extremely large resistivity reduction between ambient pressure and 10 GPa by more than 6 orders of magnitude. This decrease is among the largest reported changes in the resistivity for this narrow pressure regime. We show - by an analysis of the electronic band structure evolution of this material - that the large change in resistivity under pressure in not caused by a crossing of the bands at the Fermi level. We find that it instead stems from two bands that are pinned at the Fermi level and that are moving towards one another as a consequence of the mixed-valent to single-valent transition. This mechanism appears to be especially effective for the rapid buildup of the density of states at the Fermi level.

Spin-orbit coupling (SOC) has gained much attention for its rich physical phenomena and highly promising applications in spintronic devices. The Rashba-type SOC in systems with inversion symmetry breaking is particularly attractive for spintronics applications since it allows for flexible manipulation of spin current by external electric fields. Here, we report the discovery of a giant anisotropic Rashba-like spin splitting along three momentum directions (3D Rashba-like spin splitting) with a helical spin polarization around the M points in the Brillouin zone of trigonal layered PtBi2. Due to its inversion asymmetry and reduced symmetry at the M point, Rashba-type as well as Dresselhaus-type SOC cooperatively yield a 3D spin splitting with alpha~ 4.36 eVA in PtBi2. The experimental realization of 3D Rashba-like spin splitting not only has fundamental interests but also paves the way to the future exploration of a new class of material with unprecedented functionalities for spintronics applications., Comment: 19 pages, 5 figures

Electrocrystallization of bis(ethylenedithio)tetraselenafulvalene (BETS) and bis(ethylenedithio)tetrathiafulvalene (ET) in the presence of an electrolyte (Ph4P)[Cu(dca)]3⋅H2O [(dca) = N(CN)2] has been studied using different solvents. A new organic metal (BETS)2Cu(dca)3 (1), and the first radical cation salt with 3D dicyanamidocuprate anion, incorporating both diamagnetic Cu1+ and paramagnetic Cu2+atoms, (ET)2Cu1.8(dca)4 (2) have been obtained. Crystal structure, conducting properties of both salts, as well as the electronic structure of 2 and its structural analog (ET)2CuMn(dca)4 (3) were analysed. The salts 1 and 2 have layered structures. In contrast to the BETS radical cation salt 1, complex 2 is characterized by the presence of a 3D polymeric anion built into the ET radical cation layers. At ambient pressure, the resistance of the crystals 1 shows semimetal behaviour down to 30 K. Below 30 K, the resistance sharply increases and the sample becomes insulating. The application of a pressure of about 3 kbar suppresses the metal-insulator transition. The salt 2 undergoes a semiconductor I - semiconductor II phase transition, which is manifested by a jump in the resistance and a hysteresis in the R(T) curves in a very large temperature range (185 – 250 K). The phase transition is accompanied by changes in the charge state of the ET molecules, and notable structure changes in the anion layer, especially in the environment of Cu2+. For the salt 3 the calculated selfconsistent charges show upon cooling a sharp increase of charge order between 291 K and 285 K.

The quantum spin liquid (QSL) is a highly entangled magnetic state characterized by the absence of static magnetism in its ground state. Instead, the spins fluctuate in a highly correlated way down to the lowest temperatures. The QSL is very rare and is confined to a few specific cases where the interactions between the magnetic ions cannot be simultaneously satisfied (known as frustration). Lattices with magnetic ions in triangular or tetrahedral arrangements which interact via isotropic antiferromagnetic interactions can generate such a frustration. Three-dimensional isotropic spin liquids have mostly been sought in materials where the magnetic ions form pyrochlore or hyperkagome lattices. Here we present a three-dimensional lattice called the hyper-hyperkagome that enables spin liquid behaviour and manifests in the compound PbCuTe$_{2}$O$_{6}$. Using a combination of experiment and theory we show that this system exhibits signs of being a quantum spin liquid with no detectable static magnetism together with the presence of diffuse continua in the magnetic spectrum suggestive of fractional spinon excitations., 20 pages, 4 figures

We investigate superconductivity in ${\mathrm{In}}_{1\ensuremath{-}x}{\mathrm{Sn}}_{x}\mathrm{Te}$ ($x\ensuremath{\le}0.5$) synthesized at high pressures of up to 2 GPa and observe an enhancement of the superconducting transition temperature ${T}_{\mathrm{c}}$ for increasing tin concentration $x$. These compounds have not been accessible in rocksalt structure via conventional ambient pressure synthesis. While the lattice constant smoothly increases with $x$, ${T}_{\mathrm{c}}$ saturates around $x=0.4$. Electronic structure calculations indicate that the ${T}_{\mathrm{c}}$ modulation is brought on by the change of the density of states in the vicinity of the Fermi energy $[N({E}_{\mathrm{F}})]$. However, differences between the calculated $N({E}_{\mathrm{F}})$ and the observed electronic specific-heat coefficient indicate that the phonon dispersion plays an important role in the system and that the mechanism of superconductivity may not be the same in the entire doping range.

We investigate the stability of the spiral spin liquid phase in MnSc$_2$S$_4$ against thermal and quantum fluctuations as well as against perturbing effects of longer-range interactions. Employing $ab~initio$ density functional theory (DFT) calculations we propose a realistic Hamiltonian for MnSc$_2$S$_4$, featuring second ($J_2$) and third $(J_3)$ neighbor Heisenberg interactions on the diamond lattice that are considerably larger than previously assumed. We argue that the combination of strong $J_2$ and $J_3$ couplings reproduces the correct magnetic Bragg peak position measured experimentally. Calculating the spin-structure factor within the pseudofermion functional-renormalization group technique we find that close to the magnetic phase transition the sizable $J_3$ couplings induce a strong spiral selection effect, in agreement with experiments. With increasing temperature the spiral selection becomes weaker such that in a window around three to five times the ordering temperature an approximate spiral spin liquid is realized in MnSc$_2$S$_4$., 11 pages, 10 figures, 1 table. Published version

By applying measurements of the dielectric constants and relative length changes to the dimerized molecular conductor $\ensuremath{\kappa}\text{\ensuremath{-}}(\mathrm{BEDT}\text{\ensuremath{-}}\mathrm{TTF}{)}_{2}\mathrm{Hg}(\mathrm{SCN}{)}_{2}\mathrm{Cl}$, we provide evidence for order-disorder type electronic ferroelectricity that is driven by the charge order within the $(\mathrm{BEDT}\text{\ensuremath{-}}\mathrm{TTF}{)}_{2}$ dimers and stabilized by a coupling to the anions. According to our density functional theory calculations, this material is characterized by a moderate strength of dimerization. This system thus bridges the gap between strongly dimerized materials, often approximated as dimer-Mott systems at $1/2$ filling, and nondimerized or weakly dimerized systems at $1/4$ filling, exhibiting a charge order. Our results indicate that intradimer charge degrees of freedom are of particular importance in correlated $\ensuremath{\kappa}\text{\ensuremath{-}}(\mathrm{BEDT}\text{\ensuremath{-}}\mathrm{TTF}{)}_{2}X$ salts and can create novel states, such as electronically driven multiferroicity or charge-order-induced quasi-one-dimensional spin liquids.

Among iron chalcogenide superconductors, FeS can be viewed as a simple, highly compressed relative of FeSe without nematic phase and with weaker electronic correlations. Under pressure, however, the superconductivity of stoichiometric FeS disappears and reappears, forming two domes. We perform electronic structure and spin fluctuation theory calculations for tetragonal FeS in order to analyze the nature of the superconducting order parameter. In the random phase approximation we find a gap function with d-wave symmetry at ambient pressure, in agreement with several reports of a nodal superconducting order parameter in FeS. Our calculations show that, as a function of pressure, the superconducting pairing strength decreases until a Lifshitz transition takes place at 4.6 GPa. As a hole pocket with a large density of states appears at the Lifshitz transition, the gap symmetry is altered to sign-changing s-wave. At the same time the pairing strength is severely enhanced and increases up to a new maximum at 5.5 GPa. Therefore, our calculations naturally explain the occurrence of two superconducting domes in FeS., Comment: 6+6 pages, 4+7 figures

The series of compounds $A{\mathrm{Ag}}_{2}\mathrm{Cr}{[{\mathrm{VO}}_{4}]}_{2}$, with $A=\mathrm{Ag}$, K, or Rb, is layered S = 3/2 triangular-lattice (TL) systems in which the magnetic exchange interactions between ${\mathrm{Cr}}^{3+}\phantom{\rule{4pt}{0ex}}(3{d}^{3})$ ions are mediated by nonmagnetic ${[{\mathrm{VO}}_{4}]}^{3\ensuremath{-}}$ entities. Here, the relative orientation of the vanadate is altered with respect to the TL as a function of the $A$ site, which corresponds to an induced symmetry change of the $[{\mathrm{CrO}}_{6}]$ complex. All members of this series of compounds belong to the class of frustrated TL antiferromagnets. We find that the distorted TL ($A=\mathrm{Ag}$) exhibits collinear antiferromagnetic long-range order (LRO) at ${T}_{N}\ensuremath{\approx}10$ K, whereas the high-symmetry cases ($A=\mathrm{K}$, Rb) evade LRO in zero field down to 0.03 K, the lowest temperature of our experiments. The latter members of the series belong to the undistorted TL and are candidates for spin-liquid ground states presumably not related to Ising anisotropy or dimerization.

The insulator SrTiO3 can host high-mobility two-dimensional electron systems on its surfaces and at interfaces with other oxides. While for the bare surface a two-dimensional electron system can only be induced by oxygen vacancies, it is believed that the metallicity of heterostructure interfaces as in LaAlO3/SrTiO3 is caused by other mechanisms related to the polar discontinuity at the interface. Based on calculations using density functional and dynamical mean-field theory as well as on experimental results using photoemission spectroscopy we elucidate the role of oxygen vacancies, thereby highlighting their importance for the electronic and magnetic properties of the systems under study. Deutsche Forschungsgemeinschaft (DFG)

We investigate the electronic properties of the three-dimensional stripyhoneycomb $\ensuremath{\gamma}\text{\ensuremath{-}}{\mathrm{Li}}_{2}{\mathrm{IrO}}_{3}$ via relativistic density functional theory calculations as well as exact diagonalization of finite clusters and explore the details of the optical conductivity. Our analysis of this quantity reveals the microscopic origin of the experimentally observed (i) optical transitions and (ii) anisotropic behavior along the various polarization directions. In particular, we find that the optical excitations are overall dominated by transitions between ${j}_{\text{eff}}=1/2$ and 3/2 states and the weight of transitions between ${j}_{\text{eff}}=1/2$ states at low frequencies can be correlated to deviations from a pure Kitaev description. We furthermore reanalyze within this approach the electronic excitations in the known two-dimensional honeycomb systems $\ensuremath{\alpha}\text{\ensuremath{-}}{\mathrm{Li}}_{2}{\mathrm{IrO}}_{3}$ and ${\mathrm{Na}}_{2}{\mathrm{IrO}}_{3}$ and discuss the results in comparison to $\ensuremath{\gamma}\text{\ensuremath{-}}{\mathrm{Li}}_{2}{\mathrm{IrO}}_{3}$.

Since the discovery of high-temperature superconductivity in the thin-film $\mathrm{FeSe}/{\mathrm{SrTiO}}_{3}$ system, iron selenide and its derivates have been intensively scrutinized. Using ab initio density functional theory calculations we review the electronic structures that could be realized in iron selenide if the structural parameters could be tuned at liberty. We calculate the momentum dependence of the susceptibility and investigate the symmetry of electron pairing within the random phase approximation. Both the susceptibility and the symmetry of electron pairing depend on the structural parameters in a nontrivial way. These results are consistent with the known experimental behavior of binary iron chalcogenides and, at the same time, reveal two promising ways of tuning superconducting transition temperatures in these materials: on one hand by expanding the iron lattice of FeSe at constant iron-selenium distance and, on the other hand, by increasing the iron-selenium distance with unchanged iron lattice.

We theoretically investigate the low-temperature phase of the recently synthesized Lu$_2$Mo$_2$O$_5$N$_2$ material, an extraordinarily rare realization of a $S=1/2$ three-dimensional pyrochlore Heisenberg antiferromagnet in which Mo$^{5+}$ are the $S=1/2$ magnetic species. Despite a Curie-Weiss temperature ($\Theta_{\rm CW}$) of $-121(1)$ K, experiments have found no signature of magnetic ordering $or$ spin freezing down to $T^*\approx0.5$ K. Using density functional theory, we find that the compound is well described by a Heisenberg model with exchange parameters up to third nearest neighbors. The analysis of this model via the pseudofermion functional renormalization group method reveals paramagnetic behavior down to a temperature of at least $T=|\Theta_{\rm CW}|/100$, in agreement with the experimental findings hinting at a possible three-dimensional quantum spin liquid. The spin susceptibility profile in reciprocal space shows momentum-dependent features forming a "gearwheel" pattern, characterizing what may be viewed as a molten version of a chiral noncoplanar incommensurate spiral order under the action of quantum fluctuations. Our calculated reciprocal space susceptibility maps provide benchmarks for future neutron scattering experiments on single crystals of Lu$_2$Mo$_2$O$_5$N$_2$., Comment: Published version. Main paper (6 pages, 3 figures) + Supplemental Material (4 pages, 3 figures, 1 table)

The spinel/perovskite heterointerface $\gamma$-Al$_2$O$_3$/SrTiO$_3$ hosts a two-dimensional electron system (2DES) with electron mobilities exceeding those in its all-perovskite counterpart LaAlO$_3$/SrTiO$_3$ by more than an order of magnitude despite the abundance of oxygen vacancies which act as electron donors as well as scattering sites. By means of resonant soft x-ray photoemission spectroscopy and \textit{ab initio} calculations we reveal the presence of a sharply localized type of oxygen vacancies at the very interface due to the local breaking of the perovskite symmetry. We explain the extraordinarily high mobilities by reduced scattering resulting from the preferential formation of interfacial oxygen vacancies and spatial separation of the resulting 2DES in deeper SrTiO$_3$ layers. Our findings comply with transport studies and pave the way towards defect engineering at interfaces of oxides with different crystal structures., Comment: Accepted as Rapid Communications in Physical Review B

We study the effect of oxygen vacancies on the electronic structure of the model strongly correlated metal SrVO$_3$. By means of angle-resolved photoemission (ARPES) synchrotron experiments, we investigate the systematic effect of the UV dose on the measured spectra. We observe the onset of a spurious dose-dependent prominent peak at an energy range were the lower Hubbard band has been previously reported in this compound, raising questions on its previous interpretation. By a careful analysis of the dose dependent effects we succeed in disentangling the contributions coming from the oxygen vacancy states and from the lower Hubbard band. We obtain the intrinsic ARPES spectrum for the zero-vacancy limit, where a clear signal of a lower Hubbard band remains. We support our study by means of state-of-the-art ab initio calculations that include correlation effects and the presence of oxygen vacancies. Our results underscore the relevance of potential spurious states affecting ARPES experiments in correlated metals, which are associated to the ubiquitous oxygen vacancies as extensively reported in the context of a two-dimensional electron gas (2DEG) at the surface of insulating $d^0$ transition metal oxides., Comment: Manuscript + Supplemental Material, 12 pages, 9 figures

We present a numerical investigation of energy and charge distributions during electron-beam-induced growth of W nanostructures on SiO2 substrates using Monte Carlo simulation of electron transport. This study gives a quantitative insight into the deposition of energy and charge in the substrate and in already existing metallic nanostructures in the presence of the electron beam. We analyze electron trajectories, inelastic mean free paths, and distribution of backscattered electrons in different deposit compositions and depths. We find that, while in the early stages of the nanostructure growth a significant fraction of electron trajectories still interact with the substrate, as the nanostructure becomes thicker the transport takes place almost exclusively in the nanostructure. In particular, a larger deposit density leads to enhanced electron backscattering. This work shows how mesoscopic radiation-transport techniques can contribute to a model which addresses the multi-scale nature of the electron-beam-induced deposition (EBID) process. Furthermore, similar simulations can aid in understanding the role played by backscattered electrons and emitted secondary electrons in the change of structural properties of nanostructured materials during post-growth electron-beam treatments., Comment: 22 pages, 14 figures, 1 table

Materials with a perfect kagome lattice structure of magnetic ions are intensively sought for, because they may exhibit exotic ground states like the a quantum spin liquid phase. Barlowite is a natural mineral that features perfect kagome layers of copper ions. However, in barlowite there are also copper ions between the kagome layers, which mediate strong interkagome couplings and lead to an ordered ground state. Using {\it ab initio} density functional theory calculations we investigate whether selective isoelectronic substitution of the interlayer copper ions is feasible. After identifying several promising candidates for substitution we calculate the magnetic exchange couplings based on crystal structures predicted from first-principles calculations. We find that isoelectronic substitution with nonmagnetic ions significantly reduces the interkagome exchange coupling. As a consequence, interlayer-substituted barlowite can be described by a simple two-parameter Heisenberg Hamiltonian, for which a quantum spin liquid ground state has been predicted., contains the results on barlowite split off from arXiv:1511.05686v1

Souto, Manuel et al., There is a growing interest in the development of single-component molecular conductors based on neutral organic radicals that are mainly formed by delocalized planar radicals, such as phenalenyl or thiazolyl radicals. However, there are no examples of systems based on nonplanar and spin-localized C-centered radicals exhibiting electrical conductivity due to their large Coulomb energy (U) repulsion and narrow electronic bandwidth (W) that give rise to a Mott insulator behavior. Here we present a new type of nonplanar neutral radical conductor attained by linking a tetrathiafulvalene (TTF) donor unit to a neutral polychlorotriphenylmethyl radical (PTM) with the important feature that the TTF unit enhances the overlap between the radical molecules as a consequence of short intermolecular S···S interactions. This system becomes semiconducting upon the application of high pressure thanks to increased electronic bandwidth and charge reorganization opening the way to develop a new family of neutral radical conductors., This work was supported by the EU ITN iSwitch 642196 DGI grant (BeWell; CTQ2013-40480-R), the Networking Research Center on Bioengineering, Biomaterials, and Nanomedicine (CIBER-BBN), and the Generalitat de Catalunya (grant 2014- SGR-17). This work has also been supported by MINECO through the projects CSD2007-00045, CTQ2012- 38599-C02- 02 and CTQ2013-48252-P. ICMAB acknowledges support from the Spanish Ministry of Economy and Competitiveness, through the “Severo Ochoa” Programme for Centres of Excellence in R&D (SEV- 2015-0496). M.S. is grateful to Spanish Ministerio de Educación, Cultura y Deporte for a FPU grant and he is enrolled in the Material Science Ph.D. program of UAB. D.B. is grateful to the EC ITN Nano2fun grant no607721. M.P.A. is grateful to the Spanish Ministerio de Educación, Cultura y Deporte for an FPU grant. M.P.A. and V.G.B. thank the project CTQ2015-67755-C2-1-R. H.O. Jeschke, M. Tomic and R. Valenti thank the Deutsche Forschungsgemeinschaft (DFG) for funding through grant SFB/TRR49 and Steve Winter for useful discussions. We thank Carlos Goḿ ez-Garcıá (Univ. Valencia) for SQUID measurements as well as Xavier Fontrodona (Univ. Girona) for X-ray diffraction measurements and Mercedes Taravillo (UCM) for the support provided during the high pressure Raman measurements.

The symmetry of the superconducting order parameter in quasi-two-dimensional bis-ethylenedithio-tetrathiafulvalene (BEDT-TTF) organic superconductors is a subject of ongoing debate. We report ab initio density-functional-theory calculations for a number of organic superconductors containing $\ensuremath{\kappa}$-type layers. Using projective Wannier functions, we derive the parameters of a common low-energy Hamiltonian based on individual BEDT-TTF molecular orbitals. In a random-phase approximation spin-fluctuation approach, we investigate the evolution of the superconducting pairing symmetry within this model, and we point out a phase transition between extended $s+{d}_{{x}^{2}\ensuremath{-}{y}^{2}}$ and ${d}_{xy}$ symmetry. We discuss the origin of the mixed order parameter and the relation between the realistic molecule description and the widely used dimer approximation. Based on our ab initio calculations, we position the investigated materials in the obtained molecule model phase diagram, and we simulate scanning tunneling spectroscopy experiments for selected cases. Our calculations show that many $\ensuremath{\kappa}$-type materials lie close to the phase-transition line between the two pairing symmetry types found in our calculation, possibly explaining the multitude of contradictory experiments in this field.

We investigate the phase diagram of the spin-orbit-coupled three orbital Hubbard model at arbitrary filling by means of dynamical mean-field theory combined with continuous-time quantum Monte Carlo. We find that the spin-freezing crossover occurring in the metallic phase of the non-relativistic multiorbital Hubbard model can be generalized to a $\mathbf{J}$-freezing crossover, with $\mathbf{J}=\mathbf{L}+\mathbf{S}$, in the spin-orbit-coupled case. In the $\mathbf{J}$-frozen regime the correlated electrons exhibit a non-trivial flavor selectivity and energy dependence. Furthermore, in the regions near $n=2$ and $n=4$ the metallic states are qualitatively different from each other, which reflects the atomic Hund's third rule. Finally, we explore the appearance of magnetic order from exciton condensation at $n=4$ and discuss the relevance of our results for real materials., 13 pages, 10 figures

We present a general framework for deriving effective spin Hamiltonians of correlated magnetic systems based on a combination of relativistic ab initio density functional theory calculations, exact diagonalization of a generalized Hubbard Hamiltonian on finite clusters, and spin projections onto the low-energy subspace. A key motivation is to determine anisotropic bilinear exchange couplings in materials of interest. As an example, we apply this method to the pyrochlore ${\mathrm{Lu}}_{2}{\mathrm{V}}_{2}{\mathrm{O}}_{7}$ where the vanadium ions form a lattice of corner-sharing spin-1/2 tetrahedra. In this compound, anisotropic Dzyaloshinskii-Moriya interactions (DMIs) play an essential role in inducing a magnon Hall effect. We obtain quantitative estimates of the nearest-neighbor Heisenberg exchange, the DMI, and the symmetric part of the anisotropic exchange tensor. Finally, we compare our results with experimental ones on the ${\mathrm{Lu}}_{2}{\mathrm{V}}_{2}{\mathrm{O}}_{7}$ compound.

We present a structural analysis of the substituted system (Ba$_{1-x}$Sr$_{x}$)CuSi$_{2}$O$_{6}$, which reveals a stable tetragonal crystal structure down to 1.5 K. We explore the structural details with lowtemperature neutron and synchrotron powder diffraction, room-temperature and cryogenic highresolution NMR, as well as magnetic- and specific-heat measurements and verify that a structural phase transition into the orthorhombic structure which occurs in the parent compound BaCuSi2O6, is absent for the x = 0.1 sample. Furthermore, synchrotron powder-diffraction patterns show a reduction of the unit cell for x = 0.1 and magnetic measurements prove that the Cu-dimers are preserved, yet with a slightly reduced intradimer coupling Jintra. Pulse-field magnetization measurements reveal the emergence of a field-induced ordered state, tantamount to Bose-Einsteincondensation (BEC) of triplons, within the tetragonal crystal structure of $I\,4_{1}/acd$. This material offers the opportunity to study the critical properties of triplon condensation in a simple crystal structure.

In a common paradigm, the electronic structure of condensed matter is divided into weakly and strongly correlated compounds. While conventional band theory usually works well for the former class, many-body effects are essential for the latter. Materials like the familiar SrTiO$_3$ compound that bridge or even abandon this characterization scheme are highly interesting. Here it is shown by means of combining density functional theory with dynamical-mean field theory that oxygen vacancies on the STO (001) surface give rise to a dichotomy of weakly-correlated $t_{2g}$ low-energy quasiparticles and localized 'in-gap' states of dominant $e_g$ character with subtle correlation signature. We furthermore touch base with recent experimental work and study the surface instability towards magnetic order., 5 pages, 3 figures, supplementary material appended

In this study, we reanalyze the magnetic interactions in the Kitaev spin liquid candidate materials Na$_2$IrO$_3$, $\alpha$-RuCl$_3$, and $\alpha$-Li$_2$IrO$_3$ using nonperturbative exact diagonalization methods. These methods are more appropriate given the relatively itinerant nature of the systems suggested in previous works. We treat all interactions up to third neighbours on equal footing. The computed terms reveal significant long range coupling, bond-anisotropy, and/or off-diagonal couplings which we argue naturally explain the observed ordered phases in these systems. Given these observations, the potential for realizing the spin-liquid state in real materials is analyzed, and synthetic challenges are defined and explained.

It is demonstrated that the near-edge X-ray absorption fine structure (NEXAFS) provides a powerful local probe of functional groups in novel charge transfer (CT) compounds and their electronic properties. Microcrystals of tetra-/hexamethoxypyrene as donors with the strong acceptor tetracyano-p-quinodimethane (TMP/HMP-TCNQ) were grown by vapor diffusion. The oxygen and nitrogen K-edge spectra are spectroscopic fingerprints of the functional groups in the donor and acceptor moieties, respectively. The orbital selectivity of the NEXAFS pre-edge resonances allows us to precisely elucidate the participation of specific orbitals in the charge transfer process. Upon complex formation, the intensities of several resonances change substantially and a new resonance occurs in the oxygen K-edge spectrum. This gives evidence of a corresponding change of hybridization of specific orbitals in the functional groups of the donor (those derived from the frontier orbitals 2e and 6a(1) of the isolated methoxy group) and acceptor (orbitals b(3g), a(u), b(1g), and b(2u), all located at the cyano group) with π*-orbitals of the ring systems. Along with this intensity effect, the resonance positions associated with the oxygen K-edge (donor) and nitrogen K-edge (acceptor) shift to higher and lower photon energies in the complex, respectively. A calculation based on density functional theory qualitatively explains the experimental results. NEXAFS measurements shine light on the action of the functional groups and elucidate charge transfer on a submolecular level.