Chain Cuprate Research Articles

Unexpected magnetic phase in the weakly ordered spin- 12 chain cuprate Sr2CuO3

We present the magnetic phase diagram of a spin-1/2 chain antiferromagnet Sr$_2$CuO$_3$ studied by ultrasound phase-sensitive detection technique. We observe an enhanced effect of external magnetic field on the ordering temperature of the system, which is in the extreme proximity to the quantum critical point. Inside the N\'eel ordered phase, we detect an additional field-induced continuous phase transition, which is unexpected for a collinear Heisenberg antiferromagnet. This transition is accompanied by softening of magnetic excitation mode observed by electron-spin resonance, which can be associated with a longitudinal (amplitude) mode of the order parameter in a weakly-coupled system of spin-1/2 chains. These results suggest transition from a transverse collinear antiferromagnet to an amplitude-modulated spin density wave phase induced by magnetic field.

Highly dispersive magnons with spin-gap-like features in the frustrated ferromagneticS=12chain compoundCa2Y2Cu5O10detected by inelastic neutron scattering

We report inelastic neutron scattering experiments in Ca2Y2Cu5O10 and map out the full one magnon dispersion which extends up to a record value of 53 meV for frustrated ferromagnetic (FM) edge-sharing CuO2 chain (FFESC) cuprates. A homogeneous spin-1/2 chain model with a FM nearest-neighbor (NN), an antiferromagnetic (AFM) next-nearest-neighbor (NNN) inchain, and two diagonal AFM interchain couplings (ICs) analyzed within linear spin-wave theory (LSWT) reproduces well the observed strong dispersion along the chains and a weak one perpendicularly. The ratio R=|J_{a2}/J_{a1}| of the FM NN and the AFM NNN couplings is found as ~0.23, close to the critical point Rc=1/4 which separates ferromagnetically and antiferromagnetically correlated spiral magnetic ground states in single chains, whereas Rc>0.25 for coupled chains is considerably upshifted even for relatively weak IC. Although the measured dispersion can be described by homogeneous LSWT, the scattering intensity appears to be considerably reduced at ~11.5 and ~28 meV. The gap-like feature at 11.5 meV is attributed to magnon-phonon coupling whereas based on DMRG simulations of the dynamical structure factor the gap at 28 meV is considered to stem partly from quantum effects due to the AFM IC. Another contribution is ascribed to the intrinsic superstructure from the distorting incommensurate pattern of CaY cationic chains adjacent to the CuO2 ones. It gives rise to non-equivalent CuO4 units and Cu-O-Cu bond angles Phi and a resulting distribution of all exchange integrals. The J's fitted by homogeneous LSWT are regarded as average values. The record value of the FM NN integral J1=24 meV among FFESC cuprates can be explained by a non-universal Phi (not 90 deg.) and Cu-O bond length dependent anisotropic mean direct FM Cu-O exchange K_{pd}~120 meV. Enhanced K_{pd} values are also needed to compensate a significant AFM J_{dd} > ~6 meV.

Probing multi-spinon excitations outside of the two-spinon continuum in the antiferromagnetic spin chain cuprate Sr2CuO3

One-dimensional (1D) magnetic insulators have attracted significant interest as a platform for studying quasiparticle fractionalization, quantum criticality, and emergent phenomena. The spin-1/2 Heisenberg chain with antiferromagnetic nearest neighbour interactions is an important reference system; its elementary magnetic excitations are spin-1/2 quasiparticles called spinons that are created in even numbers. However, while the excitation continuum associated with two-spinon states is routinely observed, the study of four-spinon and higher multi-spinon states is an open area of research. Here we show that four-spinon excitations can be accessed directly in Sr2CuO3 using resonant inelastic x-ray scattering (RIXS) in a region of phase space clearly separated from the two-spinon continuum. Our finding is made possible by the fundamental differences in the correlation function probed by RIXS in comparison to other probes. This advance holds promise as a tool in the search for novel quantum states and quantum spin liquids.

Signatures of a magnetic field-induced unconventional nematic liquid in the frustrated and anisotropic spin-chain cuprate LiCuSbO4

Modern theories of quantum magnetism predict exotic multipolar states in weakly interacting strongly frustrated spin-1/2 Heisenberg chains with ferromagnetic nearest neighbor (NN) inchain exchange in high magnetic fields. Experimentally these states remained elusive so far. Here we report strong indications of a magnetic field-induced nematic liquid arising above a field of ~13 T in the edge-sharing chain cuprate LiSbCuO4 ≡ LiCuSbO4. This interpretation is based on the observation of a field induced spin-gap in the measurements of the 7Li NMR spin relaxation rate T1−1 as well as a contrasting field-dependent power-law behavior of T1−1 vs. T and is further supported by static magnetization and ESR data. An underlying theoretical microscopic approach favoring a nematic scenario is based essentially on the NN XYZ exchange anisotropy within a model for frustrated spin-1/2 chains and is investigated by the DMRG technique. The employed exchange parameters are justified qualitatively by electronic structure calculations for LiCuSbO4.

Probing inter- and intrachain Zhang-Rice excitons inLi2CuO2and determining their binding energy

Cuprate materials, such as 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 occurrence and binding energy of this quasiparticle, consisting of a pair of bound holes with antiparallel spins on the same ${\mathrm{CuO}}_{4}$ 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 ${\mathrm{CuO}}_{4}$ plaquettes in the quasi-one-dimensional chain cuprate ${\mathrm{Li}}_{2}{\mathrm{CuO}}_{2}$. 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.

Magnetic and dielectric properties of chain cuprate Li

AbstractAbstractauthoren We propose a microscopic model in order to study the multiferroic properties of LiZrCuO at low temperatures taking into account the competing nearest and next‐nearest magnetic interactions, frustration, and a linear magnetoelectric coupling. To understand the experimental observation an anti‐ferroelectric interaction between the CuO chains is included. The magnetization exhibits a peak at the antiferromagnetic transition temperature , whereas the dielectric function offers no anomaly at that temperature, however can be governed by an external magnetic field . It decreases with increasing magnetic field . Our analysis provides no indication about a glass‐like order of Li(1) discussed controversially.

Dielectric properties and electrical switching behaviour of the spin-driven multiferroic LiCuVO4

The simultaneous existence and coupling of ferroelectric and magnetic ordering in a material, so-called multiferroicity, is of great scientific interest due to the underlying complex physical mechanisms and its possible applications. Here we present the multiferroic properties of a prototypical spin-driven ferroelectric material, the spin-1/2 chain cuprate LiCuVO4. In this system, spiral spin order, with propagation in the b direction and a spin helix in the ab plane, induces ferroelectric polarization in the a direction when no magnetic field is applied. In an external magnetic field, the direction of the spin spiral and thus the direction of the electrical polarization can be switched. Broadband dielectric spectroscopy on a single crystalline sample oriented in two different directions was performed in applied external magnetic fields up to 9 T, demonstrating this switching behaviour of the ferroelectric polarization. Furthermore, detailed magnetic-field and temperature-dependent ferroelectric hysteresis-loop measurements reveal the switching of polarization by an electrical field, which implies the electric control of the spin helicity of LiCuVO4.

Magnetic structure of the frustratedS=12chain magnet LiCu2O2doped with nonmagnetic Zn

We present the results of magnetization, ESR and NMR measurements on single crystal samples of the frustrated S=1/2 chain cuprate LiCu2O2 doped with nonmagnetic Zn^2+. As shown by the x-ray techniques the crystals of Li(Cu{1-x}Zn{x})2O2 with x<0.12 are single-phase, whereas for higher Zn concentrations the samples were polyphase. ESR spectra for all monophase samples (0<= x<0.12) can be explained within the model of a planar spin structure with a uniaxial type anisotropy. The NMR spectra of the highly doped single crystal sample Li(Cu0.9Zn0.1)2O2 can be described in the frame of a planar spin glass like magnetic structure with short range spiral correlations in the crystal (ab)-planes with strongest exchange bonds. The value of magnetic moments of Cu^2+ ions in this structure is close to value obtained for undoped crystals: (0.8 +- 0.1) mu_B.

Nonstoichiometry Effect on Magnetoelectric Coupling in Cuprate Multiferroics

We present a short overview of different microscopic models for nonrelativistic and relativistic magnetoelectric coupling in 3d oxides with a particular emphasis on multiferroic properties observed in nonstoichiometric chain cuprates.

High-field NMR of the quasi-one-dimensional antiferromagnet LiCuVO4

We report on NMR studies of the quasi one--dimensional (1D) antiferromagnetic $S=1/2$ chain cuprate LiCuVO$_4$ in magnetic fields $H$ up to $\mu_0H$ = 30 T ($\approx 70$% of the saturation field $H_{\rm sat}$). NMR spectra in fields higher than $H_{\rm c2}$ ($\mu_0H_{\rm c2} \approx 7.5$ T) and temperatures $T<T_{\rm N}$ can be described within the model of a spin-modulated phase in which the magnetic moments are aligned parallel to the applied field $H$ and their values alternate sinusoidally along the magnetic chains. Based on theoretical concepts about magnetically frustrated 1D chains, the field dependence of the modulation strength of the magnetic structure is deduced from our experiments. Relaxation time $T_2$ measurements of the $^{51}$V nuclei show that $T_2$ depends on the particular position of the probing $^{51}$V nucleus with respect to the magnetic copper moments within the 1D chains: the largest $T_2$ value is observed for the vanadium nuclei which are very next to the magnetic Cu$^{2+}$ ion with largest ordered magnetic moment. This observation is in agreement with the expectation for the spin-modulated magnetic structure. The $(H,T)$ magnetic phase diagram of LiCuVO$_4$ is discussed.

Magnetic phase diagram of the frustratedS=12chain magnet LiCu2O2

We present the results of the magnetization and dielectric constant measurements on untwinned single-crystal samples of the frustrated $S=1/2$ chain cuprate LiCu${}_{2}$O${}_{2}$. Magnetic phase transitions were observed. A spin-flop transition of the spiral spin plane was observed for the field orientations $\mathbit{H}\ensuremath{\parallel}\mathbit{a}$, $\mathbit{b}$. The second magnetic transition was observed at $H\ensuremath{\approx}15$ T for all three principal field directions. This high-field magnetic phase is discussed as a collinear spin-modulated phase, which is expected for an $S=1/2$ nearest-neighbor ferromagnetic and next-nearest-neighbor antiferromagnetic chain system.

Saturation Field of Frustrated Chain Cuprates: Broad Regions of Predominant Interchain Coupling

A thermodynamic method to extract the interchain coupling (IC) of spatially anisotropic 2D or 3D spin-1/2 systems from their empirical saturation field H(s) (T=0) is proposed. Using modern theoretical methods we study how H(s) is affected by an antiferromagnetic (AFM) IC between frustrated chains described in the J(1)-J(2)-spin model with ferromagnetic 1st and AFM 2nd neighbor in-chain exchange. A complex 3D-phase diagram has been found. For Li(2)CuO(2) and Ca(2)Y(2)Cu(5)O(10), we show that H(s) is solely determined by the IC and predict H(s)≈61 T for the latter. With H(s)≈55 T from magnetization data one reads out a weak IC for Li(2)CuO(2) close to that obtained from inelastic neutron scattering.

Spin exchange dominated by charge fluctuations of the Wigner lattice in the chain cuprate Na5Cu3O6

Na5Cu3O6, a new member of one dimensional charge ordered chain cuprates, was synthesized via the azide/nitrate route by reacting NaN3, NaNO3 and CuO. According to single crystal X-ray analysis, one dimensional CuO2 chains built up from planar, edge-sharing CuO4 squares are a dominant feature of the crystal structure. From the analysis of the Cu-O bond lengths we find that the system forms a Wigner lattice. The commensurate charge order allows to explicitly assign the valence states of either +2 or +3 to each copper atom resulting in a repetition according to Cu(2+)-Cu(3+)-Cu(2+)-Cu(2+)-Cu(3+)-Cu(2+). Following the theoretical analysis of the previously synthesized compounds Na3Cu2O4 and Na8Cu5O10, the magnetic susceptibility was expected to show a large dimer gap. Surprisingly, this is not the case. To resolve this puzzle, we show that the magnetic couplings in this compound are strongly affected by excitations across the Wigner charge gap. By including these contributions, which are distinct from conventional superexchange in Mott-insulators, we obtain a quantitative satisfying theoretical description of the magnetic susceptibility data.

Heat conductivity of the spin-Peierls compounds TiOCl and TiOBr

We report experimental results on the heat conductivity \kappa of the S=1/2 spin chain compounds TiOBr and TiOCl for temperatures 5K<T<300K and magnetic fields up to 14. Surprisingly, we find no evidence of a significant magnetic contribution to \kappa, which is in stark contrast to recent results on S=1/2 spin chain cuprates. Despite this unexpected result, the thus predominantly phononic heat conductivity of these spin-Peierls compounds exhibits a very unusual behavior. In particular, we observe strong anomalies at the phase transitions Tc1 and Tc2. Moreover, we find an overall but anisotropic suppression of \kappa in the intermediate phase which extends even to temperatures higher than Tc2. An external magnetic field causes a slight downshift of the transition at Tc1 and enhances the suppression of \kappa up to Tc2. We interprete our findings in terms of strong spin-phonon coupling and phonon scattering arising from spin-driven lattice distortions.

NMR study of the high-field magnetic phase ofLiCuVO4

We report on NMR studies of the quasi--1D antiferromagnetic $S=1/2$ chain cuprate LiCuVO$_4$, focusing on the high--field spin--modulated phase observed recently in applied magnetic fields $H > H_{\rm c2}$ ($\mu_0H_{\rm c2} \approx 7.5$ T). The NMR spectra of $^7$Li and $^{51}$V around the transition from the ordered to the paramagnetic state were measured. It is shown that the spin--modulated magnetic structure forms with ferromagnetic interactions between spins of neighboring chains within the {\bf ab}--plane at low temperatures 0.6 K $ < T < T_{\rm N}$. The best fit provides evidence that the mutual orientation between spins of neighboring {\bf ab}--planes is random. For elevated temperatures $T_{\rm N} < T \lesssim 15$ K, short--range magnetic order occurs at least on the characteristic time scale of the NMR experiment.

Ballistic heat transport of quantum spin excitations as seen inSrCuO2

Fundamental conservation laws predict ballistic, i.e., dissipationless transport behaviour in one-dimensional quantum magnets. Experimental evidence, however, for such anomalous transport has been lacking ever since. Here we provide experimental evidence for ballistic heat transport in a S=1/2 Heisenberg chain. In particular, we investigate high purity samples of the chain cuprate SrCuO2 and observe a huge magnetic heat conductivity $\kappa_{mag}$. An extremely large spinon mean free path of more than a micrometer demonstrates that $\kappa_{mag}$ is only limited by extrinsic scattering processes which is a clear signature of ballistic transport in the underlying spin model.

Progress in the theoretical description of a strongly frustrated edge-shared model chain cuprate: Li2CuO2

We report an essentially improved microscopic understanding of the leading in-chain NN and NNN exchange integrals J1 and J2 for the prototype title compound. It is based on a novel analysis of the optical conductivity σ(ω,T) within a five-band extended Hubbard model the O 1s x-ray absorption and other spectroscopic data using exact diagonalizations, the DMRG technique, and L(S)DA+U calculations, as well as a spin-wave fit of new inelastic neutron data for Li2CuO2. Here a highly dispersive magnetic excitation has been detected for the first time. It gives rise to a more than twice as large ferromagnetic J1 ~ −230 K and to a smaller in-chain frustration ratio − J2/J1 = 0.33 ± 0.01 as compared with the results based on a different microscopic parameter set proposed by Mizuno et al. 1998 Phys. Rev. B 57 5326. The frustrated inter-chain interaction is found to be responsible for the FM ordering.

Analysis of the magnetic response of the edge-sharing chain cuprate Li2CuO2 within TMRG

It is widely accepted that the low-energy physics in edge-sharing cuprate materials has one-dimensional (1D) character. The relevant model to study such systems is believed to be the 1D extended Heisenberg model with ferromagnetic nearest-neighbor (NN) interaction and antiferromagnetic next-nearest-neighbor one. Thus far, however, theoretical studies of such materials have been confined to the case of isotropic interactions. In the present work, we compare the spin susceptibility of the 1D extended Heisenberg model with anisotropy in the NN channel, obtained by means of the Transfer Matrix Renormalization Group method, with that of the edge-sharing chain cuprate Li2CuO2.

Electronic structure and magnetic properties ofLi2ZrCuO4: A spin-12Heisenberg system close to a quantum critical point

Based on density functional calculations, we present a detailed theoretical study of the electronic structure and the magnetic properties of the quasi-one dimensional chain cuprate Li_2ZrCuO_4 (Li_2CuZrO_4). For the relevant ratio of the next-nearest neighbor exchange J_2 to the nearest neighbor exchange J_1 we find alpha = -J_2/J_1 = 0.22\pm0.02 which is very close to the critical point at 1/4. Owing this vicinity to a ferromagnetic-helical critical point, we study in detail the influence of structural peculiarities such as the reported Li disorder and the non-planar chain geometry on the magnetic interactions combining the results of LDA based tight-binding models with LDA+U derived exchange parameters. Our investigation is complemented by an exact diagonalization study of a multi-band Hubbard model for finite clusters predicting a strong temperature dependence of the optical conductivity for Li_2ZrCuO_4.

Electron localization into a bound spin polaron in the quasi-one-dimensionalS=12antiferromagnetLiCu2O2

Muon spin rotation experiments in zero magnetic field and magnetization measurements have been carried out in a single crystal of spin $S=1/2$ double chain cuprate ${\text{LiCu}}_{2}{\text{O}}_{2}$ over a temperature range of 2--300 K. In the antiferromagnetic state we find a bound state of an electron around the muon---the magnetic polaron---with the electron wave function confined within $R=0.55\ifmmode\pm\else\textpm\fi{}0.05\text{ }\text{nm}$. Electron localization in this form persists up to 31 K, well above ${T}_{N}=24.7\text{ }\text{K}$.