Interplay of lattice-spin-orbital coupling and Jahn-Teller effect in noncollinear spinel TixMn1-x(FeyCo1-y)2O4: a neutron diffraction study.

Local magnetostructural changes and dynamical spin fluctuations in doubly diluted spinel TixMn1‒x(FeyCo1‒y)2O4has been reported by means of neutron diffraction and magnetization studies. Two distinct sets of compositions (i)x(Ti) = 0.20 andy(Fe) = 0.18; (ii)x(Ti) = 0.40 andy(Fe) = 0.435 have been considered for this study. The first compound of equivalent stoichiometry Ti0.20Mn0.80Fe0.36Co1.64O4exhibits enhanced tetragonal distortion across the ferrimagnetic transition temperatureTC= 258 K in comparison to the end compound MnCo2O4(TC∼ 180 K) with a characteristic ratioct/√2atof 0.99795(8) demonstrating robust lattice-spin-orbital coupling. However, in the second case Ti0.40Mn0.60Fe0.87Co1.13O4with higherB-site compositions, the presence of Jahn-Teller ions with distinct behavior appears to counterbalance the strong tetragonal distortion thereby ceasing the lattice-spin-orbital coupling. Both the investigated systems show the coexistence of noncollinear antiferromagnetic and ferrimagnetic components in cubic and tetragonal settings. On the other hand, the dynamical ac-susceptibility,χac(T) reveals a cluster spin-glass state with Gabay-Toulouse (GT) like mixed phases behaviour belowTC. Such dispersive behaviour appears to be sensitive to the level of octahedral substitution. Further, the field dependence ofχac(T) follows the weak anisotropic GT-line behaviour with crossover exponent Φ lies in the range 1.38-1.52 on theH-Tplane which is in contrast to theB-site Ti substituted MnCo2O4spinel that appears to follow irreversible non-mean-field AT-line behaviour (Φ âˆ¼ 3 +δ). Finally, the Arrott plots analysis indicates the presence of a pseudo first-order like transition (T< 20 K) which is in consonance with and zero crossover of the magnetic entropy change within the frozen spin-glass regime.

Spin-liquid state with precursor ferromagnetic clusters interacting antiferromagnetically in frustrated glassy tetragonal spinel Zn0.8Cu0.2FeMnO4.

Spinels (AB2O4) with magnetic ions occupying only the octahedralBsites have inherent magnetic frustration which inhibits magnetic long-range order (LRO) but may lead to exotic states. Here we report on the magnetic properties of the tetragonal spinel Zn0.8Cu0.2FeMnO4, the tetragonality resulting from the Jahn-Teller active Mn3+ions. X-ray diffraction and x-ray photoelectron spectroscopy of the sample yielded the composition (Zn0.82+Cu0.22+)A[Fe0.42+Fe0.63+Mn3+]BO4‒δ. Analysis of the temperature dependence of magnetization (M), ac magnetic susceptibilities (χ'andχ''), dc susceptibility (χ), heat capacityCp, and neutron diffraction (ND) measurements show complex temperature-dependent short-range order (SRO) but without LRO. The data ofχ vs. Tfits the Curie-Weiss law:χ = C/(T ‒ θ) fromT= 250 K to 400 K withθ≃ 185 K signifying dominant ferromagnetic (FM) coupling with the FM exchange constantJ/kB= 17 K, andC= 3.29 emu K mol‒1Oe‒1yielding an effective magnetic momentµeff= 5.13µBresulting from the high-spin states of Cu2+(Asite) and Fe2+(Bsite), while theBsite trivalent ions Mn3+and Fe3+are in their low-spin states. The extrapolated saturation magnetization obtained from theM vs. Hdata atT= 2 K is explained using the spin arrangement (Cu2+↓)A[Fe2+↑, Fe3+↓, Mn3+↑]Bleading to FM clusters interact antiferromagnetically at low temperatures. Temperature dependence of d(χT)/dTshows the onset of ferrimagnetism below ∼100 K and peaks near 47 K and 24 K. The relaxation timeτobtained from temperature and frequency dependence ofχ″when fit to the power law and Vogel-Fulcher laws confirm the cluster spin-glass (SG) state. The magnetic field dependence of the SG temperatureTSGHfollows the equation:TSGH=TSG01-AH2/ϕwithTSG(0) = 46.6 K,A= 8.6 × 10‒3Oe‒0.593andϕ= 3.37. The temperature dependence of hysteresis loops yields coercivityHC∼ 3.8 kOe at 2 K without exchange-bias, butHCdecreases with increase inTbecoming zero above 24 K, theTSG(H) forH= 800 Oe. Variations ofCpvs. Tfrom 2 K to 200 K inH=0 andH=90 kOe do not show any peak characteristic of LRO. However, after correcting for the lattice contribution, a broad weak peak typically of SRO becomes evident centered around 40 K. ForT< 9 K,Cpvaries asT2; a typical signature of spin-liquids (SLs). Comparison of the ND measurements at 1.7 K and 79.4 K shows absence of LRO. Time dependence of thermo-remanent magnetizationMTRM(t) studies below 9 K reveal weakening of the inter-cluster interaction with increase in temperature. A summary of these results is that in Zn0.8Cu0.2FeMnO4, ferromagnetic clusters interact antiferromagnetically without LRO but producing a cluster SG state atTSG(0) = 46.6 K, followed by SL behavior below 9 K.

Magnetic-field induced melting of long-range magnetic order akin to Kitaev insulators in the metallic compound Tb5Si3.

There have been constant efforts to find 'exotic' quantum spin-liquid (QSL) materials. Some of the transition metal insulators dominated by the direction-dependent anisotropic exchange interaction ('Kitaev model' for honeycomb network of magnetic ions) are considered to be promising cases for the same. In such Kitaev insulators, QSL is achieved from the zero-field antiferromagnetic state by the application of magnetic-field, suppressing other exchange interactions responsible for magnetic order. Here, we show that the features attributable to long-range magnetic ordering of the intermetallic compound, Tb5Si3, (TN= 69 K), containing honey-comb network of Tb ions, are completely suppressed by a critical applied field,Hcr, in heat-capacity and magnetization data, mimicking the behavior of Kitaev physics candidates. The neutron diffraction patterns as a function ofHreveal that it is an incommensurate magnetic structure that gets suppressed, showing peaks arising from multiple wave vectors beyondHcr. Increasing magnetic entropy as a function ofHwith a peak in the magnetically ordered state is in support of some kind of magnetic disorder in a narrow field range afterHcr. Such a high-field behavior for a metallic heavy rare-earth system to our knowledge has not been reported in the past and therefore is intriguing.

Magnetization Process of Atacamite: A Case of Weakly Coupled S=1/2 Sawtooth Chains.

We present a combined experimental and theoretical study of the mineral atacamite Cu_{2}Cl(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_{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.

Neutron diffraction evidence for local spin canting, weak Jahn-Teller distortion, and magnetic compensation in Ti1-x Mn x Co2O4 spinel.

A systematic study using neutron diffraction and magnetic susceptibility is reported on Mn substituted ferrimagnetic inverse spinel Ti1-x Mn x Co2O4 in the temperature interval 1.6 K [Formula: see text] T [Formula: see text] 300 K. Our neutron diffraction study reveals cooperative distortions of the TO6 octahedra in the Ti1-x Mn x Co2O4 system for all the Jahn-Teller active ions T = Mn3+ , Ti3+ and Co3+ , having the electronic configurations 3d 1, 3d 4 and 3d 6, respectively which are confirmed by the x-ray photoelectron spectroscopy. Two specific compositions (x = 0.2 and 0.4) have been chosen in this study because these two systems show unique features such as; (i) noncollinear Yafet-Kittel type magnetic ordering, and (ii) weak tetragonal distortion with c/a < 1, in which the apical bond length d c (T B -O) is longer than the equatorial bond length d ab (T B -O) due to the splitting of the e g level of Mn3+ ions into [Formula: see text] and [Formula: see text]. For the composition x = 0.4, the distortion in the T B O6 octahedra is stronger as compared to x = 0.2 because of the higher content of trivalent Mn. Ferrimagnetic ordering in Ti0.6Mn0.4Co2O4 and Ti0.8Mn0.2Co2O4 sets in at 110.3 and 78.2 K, respectively due to the presence of unequal magnetic moments of cations, where Ti3+ , Mn3+ , and Co3+ occupy the octahedral, whereas, Co2+ sits in the tetrahedral site. For both compounds an additional weak antiferromagnetic component could be observed lying perpendicular to the ferrimagnetic component. The analysis of static and dynamic magnetic susceptibilities combined with the heat-capacity data reveals a magnetic compensation phenomenon (MCP) at T COMP = 25.4 K in Ti0.8Mn0.2Co2O4 and a reentrant spin-glass behaviour in Ti0.6Mn0.4Co2O4 with a freezing temperature of ∼110.1 K. The MCP in this compound is characterized by sign reversal of magnetization and bipolar exchange bias effect below T COMP with its magnitude depending on the direction of external magnetic field and the cooling protocol.

Orbital Glass State of the Nearly Metallic Spinel Cobalt Vanadate.

Strain, magnetization, dielectric relaxation, and unpolarized and polarized neutron diffraction measurements were performed to study the magnetic and structural properties of spinel Co_{1-x}V_{2+x}O_{4}. The strain measurement indicates that, upon cooling, ΔL/L in the order of ∼10^{-4} starts increasing below T_{C}, becomes maximum at T_{max}, and then decreases and changes its sign at T^{*}. Neutron measurements indicate that a collinear ferrimagnetic order develops below T_{C} and upon further cooling noncollinear ferrimagnetic ordering occurs below T_{max}. At low temperatures, the dielectric constant exhibits a frequency dependence, indicating slow dynamics. These results indicate the existence of an orbital glassy state at low temperatures in this nearly metallic frustrated magnet.

Complex Field-Induced States in Linarite PbCuSO4(OH)2 with a Variety of High-Order Exotic Spin-Density Wave States.

Low-temperature neutron diffraction and NMR studies of field-induced phases in linarite are presented for magnetic fields H∥b axis. A two-step spin-flop transition is observed, as well as a transition transforming a helical magnetic ground state into an unusual magnetic phase with sine-wave-modulated moments ∥H. An effective J[over ˜]_{1}-J[over ˜]_{2} single-chain model with a magnetization-dependent frustration ratio α_{eff}=-J[over ˜]_{2}/J[over ˜]_{1} is proposed. The latter is governed by skew interchain couplings and shifted to the vicinity of the ferromagnetic critical point. It explains qualitatively the observation of a rich variety of exotic longitudinal collinear spin-density wave, SDW_{p}, states (9≥p≥2).

Competing exchange interactions on the verge of a metal-insulator transition in the two-dimensional spiral magnet Sr3Fe2O7.

We report a neutron scattering study of the magnetic order and dynamics of the bilayer perovskite Sr(3)Fe(2)O(7), which exhibits a temperature-driven metal-insulator transition at 340 K. We show that the Fe(4+) moments adopt incommensurate spiral order below T(N) = 115 K and provide a comprehensive description of the corresponding spin-wave excitations. The observed magnetic order and excitation spectra can be well understood in terms of an effective spin Hamiltonian with interactions ranging up to third-nearest-neighbor pairs. The results indicate that the helical magnetism in Sr(3)Fe(2)O(7) results from competition between ferromagnetic double-exchange and antiferromagnetic superexchange interactions whose strengths become comparable near the metal-insulator transition. They thus confirm a decades-old theoretical prediction and provide a firm experimental basis for models of magnetic correlations in strongly correlated metals.

FeCr2S4 in magnetic fields: possible evidence for a multiferroic ground state.

We report on neutron diffraction, thermal expansion, magnetostriction, dielectric, and specific heat measurements on polycrystalline FeCr2S4 in external magnetic fields. The ferrimagnetic ordering temperatures TC ≈ 170 K and the transition at TOO ≈ 10 K, which has been associated with orbital ordering, are only weakly shifted in magnetic fields up to 9 T. The cubic lattice parameter is found to decrease when entering the state below TOO. The magnetic moments of the Cr- and Fe-ions are reduced from the spin-only values throughout the magnetically ordered regime, but approach the spin-only values for fields >5.5 T. Thermal expansion in magnetic fields and magnetostriction experiments indicate a contraction of the sample below about 60 K. Below TOO this contraction is followed by a moderate expansion of the sample for fields larger than ~4.5 T. The transition at TOO is accompanied by an anomaly in the dielectric constant. The dielectric constant depends on both the strength and orientation of the external magnetic field with respect to the applied electric field for T < TOO. A linear correlation of the magnetic-field-induced change of the dielectric constant and the magnetic-field dependent magnetization is observed. This behaviour is consistent with the existence of a ferroelectric polarization and a multiferroic ground state below 10 K.

Magnetic frustration in a quantum spin chain: the case of linarite PbCuSO4(OH)2.

We present a combined neutron diffraction and bulk thermodynamic study of the natural mineral linarite PbCuSO4(OH)2, this way establishing the nature of the ground-state magnetic order. An incommensurate magnetic ordering with a propagation vector k=(0,0.186,1/2) was found below T(N)=2.8 K in a zero magnetic field. The analysis of the neutron diffraction data yields an elliptical helical structure, where one component (0.638µ(B)) is in the monoclinic ac plane forming an angle with the a axis of 27(2)°, while the other component (0.833µ(B)) points along the b axis. From a detailed thermodynamic study of bulk linarite in magnetic fields up to 12 T, applied along the chain direction, a very rich magnetic phase diagram is established, with multiple field-induced phases, and possibly short-range-order effects occurring in high fields. Our data establish linarite as a model compound of the frustrated one-dimensional spin chain, with ferromagnetic nearest-neighbor and antiferromagnetic next-nearest-neighbor interactions. Long-range magnetic order is brought about by interchain coupling 1 order of magnitude smaller than the intrachain coupling.

Anisotropy of extinction: extrapolation to the kinematical limit by γ-ray diffraction.

A direct experimental approach to the problem of anisotropic extinction is presented. Structure-factor measurements from a vanadium and a niobium crystal, performed with four γ-ray wavelengths in the range 0.02-0.06 Å, substantiate the adequacy of Zachariasen's theory [Acta Cryst. (1967), 23, 558-564] in high-energy diffraction, which provides a theoretical basis for the extrapolation to zero extinction values. Fitting of the theoretical curve to the observed points, placed on a common scale, allows determination of the kinematical structure-factor value without the need for a particular model of anisotropy in the mosaic structure.

From (pi,0) magnetic order to superconductivity with (pi,pi) magnetic resonance in Fe(1.02)Te(1-x)Se(x).

The iron chalcogenide Fe(1+y)(Te(1-x)Se(x)) is structurally the simplest of the Fe-based superconductors. Although the Fermi surface is similar to iron pnictides, the parent compound Fe(1+y)Te exhibits antiferromagnetic order with an in-plane magnetic wave vector (pi,0) (ref. 6). This contrasts the pnictide parent compounds where the magnetic order has an in-plane magnetic wave vector (pi,pi) that connects hole and electron parts of the Fermi surface. Despite these differences, both the pnictide and chalcogenide Fe superconductors exhibit a superconducting spin resonance around (pi,pi) (refs 9, 10, 11). A central question in this burgeoning field is therefore how (pi,pi) superconductivity can emerge from a (pi,0) magnetic instability. Here, we report that the magnetic soft mode evolving from the (pi,0)-type magnetic long-range order is associated with weak charge carrier localization. Bulk superconductivity occurs as magnetic correlations at (pi,0) are suppressed and the mode at (pi, pi) becomes dominant for x>0.29. Our results suggest a common magnetic origin for superconductivity in iron chalcogenide and pnictide superconductors.

Magnetic structure of RuSr2GdCu2O8 determined by resonant x-ray diffraction.

X-ray diffraction with photon energies near the Ru L2-absorption edge was used to detect resonant reflections characteristic of a G-type superstructure in RuSr2GdCu2O8 single crystals. A polarization analysis confirms that these reflections are due to magnetic order of Ru moments, and the azimuthal-angle dependence of the scattering amplitude reveals that the moments lie along a low-symmetry axis with substantial components parallel and perpendicular to the RuO2 layers. Complemented by susceptibility data and a symmetry analysis of the magnetic structure, these results reconcile many of the apparently contradictory findings reported in the literature.

Incommensurate spin-density modulation in a copper oxide chain compound with commensurate charge order.

Neutron diffraction has been used to determine the magnetic structure of Na8Cu5O10, a stoichiometric compound containing chains based on edge-sharing CuO4 plaquettes. The chains are doped with 2/5 hole per Cu site and exhibit long-range commensurate charge order with an onset well above room temperature. Below TN=23 K, the neutron data indicate long-range collinear magnetic order with a spin-density modulation whose propagation vector is commensurate along, and incommensurate perpendicular to, the chains. Competing interchain exchange interactions are discussed as a possible origin of the incommensurate magnetic order.

One- and two-triplon spectra of a cuprate ladder.

We have performed inelastic neutron scattering on the near ideal spin-ladder compound La4Sr10Cu24O41 as a starting point for investigating doped ladders and their tendency toward superconductivity. A key feature was the separation of one-triplon and two-triplon scattering. Two-triplon scattering is observed quantitatively for the first time and so access is realized to the important strong magnetic quantum fluctuations. The spin gap is found to be 26.4+/-0.3 meV. The data are successfully modeled using the continuous unitary transformation method, and the exchange constants are determined by fitting to be Jleg=186 meV and Jrung=124 meV along the leg and rung, respectively; a substantial cyclic exchange of Jcyc=31 meV is confirmed.

Electron-density distribution in cubic SrTiO3: a comparative gamma-ray diffraction study.

The electron density and atomic displacements in the perovskite SrTiO(3) have been studied using extensive and accurate gamma-ray diffraction data (lambda = 0.0392 A) at room temperature. The six strongest low-order structure factors have been determined under extinction-free conditions. Gram-Charlier series expansion of the thermal parameters have revealed no evidence for anharmonicity. The population of the 3d subshell on Ti is found to be close to zero, in agreement with the observed magnetic behaviour. The electronic properties at the bond critical points indicate ionic Ti-O and Sr-O interactions of different strengths, which is corroborated by the net charges of the atomic basins [q(Sr) = 1.18 |e|, q(Ti) = 3.10 |e|, q(O) = -1.42 |e|]. A critical comparison is made with earlier experimental results from laboratory X-ray, synchrotron X-ray, electron and neutron diffraction studies. Agreement and discrepancies are identified and resolved.

Gamma-ray and neutron diffraction studies of CoF2: magnetostriction, electron density and magnetic moments.

Accurate structure factors up to sin theta/lambda = 1.6 A(-1) have been measured with 316.5 keV gamma-rays from CoF(2), both at room temperature and in the antiferromagnetic state at 10 K. The same crystal was used to collect extended time-of-flight neutron diffraction data in the two magnetic states, which allowed an accurate determination of the fluorine positional parameter. For room temperature, the standard structural parameters are reported. At 10 K, a complete charge-density study has been carried out. The total number of 3d electrons on Co is found to be 6.95 (3). The experimental populations of the d orbitals agree with expectation from crystal field theory. The fluorine valence region exhibits a strong dipolar deformation. Electronic properties at the bond critical points and integrated atomic properties are derived from the static model electron density, revealing the Co-F interactions as purely ionic. On magnetic ordering, a shift of the fluorine ions of 1.5 (4) x 10(-3) A is found which confirms a prediction from theory of optical birefringence. The effect of magnetostriction on the distortion of the ligand coordination octahedra is compared for the late members of the 3d transition-metal difluorides. From neutron powder diffraction, an ordered magnetic moment of 2.60 (4) mu(B) per cobalt ion is found. Despite the strong deviation from the ideal spin value of 3 mu(B), there is still an appreciable orbital contribution to the local magnetic moment.

Magnetic neutron scattering study of YVO3: evidence for an orbital Peierls state.

Neutron spectroscopy has revealed a highly unusual magnetic structure and dynamics in YVO3, an insulating pseudocubic perovskite that undergoes a series of temperature-induced phase transitions between states with different spin and orbital ordering patterns. A good description of the neutron data is obtained by a theoretical analysis of the spin and orbital correlations of a quasi-one-dimensional model. This leads to the tentative identification of one of the phases of YVO3 with the "orbital Peierls state," a theoretically proposed many-body state comprised of orbital singlet bonds.

Magnetic order and dynamics in an orbitally degenerate ferromagnetic insulator.

Neutron scattering was used to determine the spin structure and the magnon spectrum of the Mott-Hubbard insulator YTiO3. The magnetic structure is complex, comprising substantial G-type and A-type antiferromagnetic components in addition to the predominant ferromagnetic component. The magnon spectrum, on the other hand, is gapless and nearly isotropic. We show that these findings are inconsistent with the orbitally ordered states thus far proposed for YTiO3 and discuss general implications for a theoretical description of exchange interactions in orbitally degenerate systems.

Anharmonicity of potentials of atoms in potassium hydrogensulfide (KDS) determined by neutron single-crystal diffraction

Potassium hydrogensulfide (KHS) is an ionic compound with an anionic molecular group HS(-). The fast reorientational disorder of the anions was determined for the ambient temperature modification [R3;m; Jeffrey (1974). Can. J. Phys. 52, 2370-2378]. Single crystals are available now as protonated or deuterated specimens. With neutron single-crystal diffraction at room temperature, a considerable anharmonicity of the atom potential of the H or D atoms was observed. Even the thermal motions of K and S atoms show small deviations from an isotropic probability density function, which can be modelled using anharmonic temperature factors. The temperature factors of the atoms were expanded into a Gram-Charlier series [Kuhs (1992). Acta Cryst. A48, 80-98] in order to evaluate the anharmonicity quantitatively. Parameters up to a fourth-order approximation are relevant for the D atoms. Results from neutron single-crystal diffraction are compared with split-atom models extracted from neutron powder diffraction patterns of fully deuterated samples.