Orbital ordering and spin-ladder formation in La2RuO5

The semiconductor-semiconductor transition of La2RuO5 is studied by means of augmented spherical wave electronic structure calculations as based on density-functional theory and the local density approximation. This transition has lately been reported to lead to orbital ordering and a quenching of the local spin magnetic moment. Our results hint towards an orbital ordering scenario which, markedly different from the previously proposed scheme, preserves the local S=1 moment at the Ru sites in the low-temperature phase. The unusual magnetic behavior is interpreted by the formation of spin ladders, which result from the structural changes occurring at the transition and are characterized by antiferromagnetic coupling along the rungs.     

Pressure-tuned collapse of the Mott-like state in Ca(n+1)Ru(n)O(3n+1) (n=1,2): Raman spectroscopic studies

We report a Raman scattering study of the pressure-induced collapse of the Mott-like phases of Ca3Ru2O7 (T(N)=56 K) and Ca2RuO4 (T(N)=110 K). The pressure dependence of the phonon and two-magnon excitations in these materials indicate (i) a T approximately 0 pressure-induced collapse of the antiferromagnetic (AF) insulating phase above P(*) approximately 55 kbar in Ca3Ru2O7 and P(*) approximately 5-10 kbar in Ca2RuO4, (ii) a remarkable insensitivity of the exchange interaction to pressure in both systems, and (iii) evidence for persistent AF correlations above the critical pressure of Ca2RuO4, suggestive of phase separation involving AF insulator and ferromagnetic metal phases.     

Novel orbital ordering induced by anisotropic stress in a manganite thin film

A novel structure of orbital ordering is found in a Nd0.5Sr0.5MnO3 thin film, which exhibits a clear first-order transition, by synchrotron x-ray diffraction measurements. Lattice parameters vary drastically at the metal-insulator transition at 170 K (= T(MI)), and superlattice reflections appear below 140 K (= T(CO)). The electronic structure between T(MI) and T(CO) is identified as A-type antiferromagnetic with a d(x2-y2) ferro-orbital ordering. The new type of antiferro-orbital ordering characterized by the wave vector (1/4 1/4 1/2) in cubic notation emerges below T(CO). The accommodation of the large lattice distortion at the first-order phase transition and the appearance of the novel orbital ordering are brought about by the anisotropy in the substrate, a new parameter for the phase control.     

Change of electronic structure in Ca2RuO4 induced by orbital ordering

Optical conductivity spectra sigma(omega) were used to investigate the effect of orbital ordering on the electronic structure of Ca2RuO4. Our LDA+U calculation predicts Ru 4d(xy) ferro-orbital ordering at the ground state, and well explains the present sigma(omega) as well as the reported O 1s x-ray absorption spectra. Variation of temperature (T) causes a large change of spectral weight over several eV as well as collapse of a charge gap accompanied by elongation of the c-axis Ru-O bond length. These results clearly indicate that the d(xy) orbital ordering plays a crucial role in the metal-insulator transition and the T-dependent electronic structure on a large energy scale.     

Spin-orbit coupling in the Mott insulator Ca(2)RuO(4)

O 1s x-ray absorption study of the Mott insulator Ca(2)RuO(4) shows that the orbital population of the 4d t(2g) band dramatically changes with temperature. In addition, spin-resolved circularly polarized photoemission study of Ca(2)RuO(4) shows that a substantial orbital angular momentum is induced in the Ru 4d t(2g) band. Based on the experimental results and model Hartree-Fock calculations, we argue that the cooperation between the strong spin-orbit coupling in the Ru 4d t(2g) band and the small distortion of the RuO(6) octahedra causes the interesting changeover of the spin and orbital anisotropy as a function of temperature.     

Orbitally driven spin-singlet dimerization in S=1 La4Ru2O10

Using x-ray absorption spectroscopy at the Ru-L2,3 edge we reveal that the Ru4+ ions remain in the S=1 spin state across the rare 4d-orbital ordering transition and spin-gap formation. We find using local spin density approximation + Hubbard U band structure calculations that the crystal fields in the low-temperature phase are not strong enough to stabilize the S=0 state. Instead, we identify a distinct orbital ordering with a significant anisotropy of the antiferromagnetic exchange couplings. We conclude that La4Ru2O10 appears to be a novel material in which the orbital physics drives the formation of spin-singlet dimers in a quasi-two-dimensional S=1 system.     

Negative volume thermal expansion via orbital and magnetic orders in Ca₂Ru₁-(x)Cr(x)O₄(0 < x < 0.13)

Ca?RuO? undergoes a metal-insulator transition at T(MI)=357 K, followed by a well-separated transition to antiferromagnetic order at T(N)=110 K. Dilute Cr doping for Ru reduces the temperature of the orthorhombic distortion at T(MI) and induces ferromagnetic behavior at T(C). The lattice volume V of Ca?Ru?-(x)Cr(x)O? (0 < x < 0.13) abruptly expands with cooling at both T(MI) and T(C), giving rise to a total volume expansion ΔV/V ≈ 1%, which sharply contrasts the smooth temperature dependence of the few known examples of negative volume thermal expansion driven by anharmonic phonon modes. In addition, the near absence of volume thermal expansion between T(C) and T(MI) represents an Invar effect. The two phase transitions, which surprisingly mimic the classic freezing transition of water, suggest an exotic ground state driven by an extraordinary coupling between spin, orbit, and lattice degrees of freedom.     

Evidence for electronic phase separation between orbital orderings in SmVO3

We report evidence for phase coexistence of orbital orderings of different symmetry in SmVO3 by high resolution x-ray powder diffraction. The phase coexistence is triggered by an antiferromagnetic ordering of the vanadium spins near 130 K, below an initial orbital ordering near 200 K. The phase coexistence is the result of the intermediate ionic size of samarium coupled to exchange striction at the vanadium spin ordering.     

Fermi surface topology of Ca1.5Sr0.5RuO4 determined by angle-resolved photoelectron spectroscopy

We report angle-resolved photoelectron spectroscopy results of the Fermi surface of Ca1.5Sr0.5RuO4, which is at the boundary of magnetic/orbital instability in the phase diagram of the Ca-substituted Sr ruthenates. Three t(2g) energy bands and the corresponding Fermi surface sheets are observed, which are also present in the Ca-free Sr2RuO4. We find that while the Fermi surface topology of the alpha,beta (d(yz,zx)) sheets remains almost the same in these two materials, the gamma (d(xy)) sheet exhibits a holelike Fermi surface in Ca1.5Sr0.5RuO4 in contrast to being electronlike in Sr2RuO4. Our observation of all three volume conserving Fermi surface sheets clearly demonstrates the absence of orbital-selective Mott transition, which was proposed theoretically to explain the unusual transport and magnetic properties in Ca1.5Sr0.5RuO4.     

Neutron diffraction and electrical transport studies on the incommensurate magnetic phase transition in holmium at high pressures

Neutron diffraction and electrical transport measurements have been made on the heavy rare earth metal holmium at high pressures and low temperatures in order to elucidate its transition from a paramagnetic (PM) to a helical antiferromagnetic (AFM) ordered phase as a function of pressure. The electrical resistance measurements show a change in the resistance slope as the temperature is lowered through the antiferromagnetic Néel temperature. The temperature of this antiferromagnetic transition decreases from approximately 122 K at ambient pressure at a rate of -4.9 K GPa(-1) up to a pressure of 9 GPa, whereupon the PM-to-AFM transition vanishes for higher pressures. Neutron diffraction measurements as a function of pressure at 89 and 110 K confirm the incommensurate nature of the phase transition associated with the antiferromagnetic ordering of the magnetic moments in a helical arrangement and that the ordering occurs at similar pressures as determined from the resistance results for these temperatures.     

Microstrain sensitivity of orbital and electronic phase separation in SrCrO3

An orbital ordering transition and electronic phase coexistence have been discovered in SrCrO3. This cubic, orbitally-degenerate perovskite transforms to a tetragonal phase with partial orbital order. The tetragonal phase is antiferromagnetic below 35-40 K, whereas the cubic phase remains paramagnetic at low temperatures. The orbital ordering temperature (35-70 K) and coexistence of the two electronic phases are very sensitive to lattice strain. X-ray measurements show a preferential conversion of the most strained regions in the cubic phase. This reveals that small fluctuations in microstrain are sufficient to drive long range separation of competing electronic phases even in undoped cubic oxides.     

Manifestations of broken symmetry: the surface phases of Ca(2-x)SrxRuO4

The surface structural phases of Ca(2-x)SrxRuO4 are investigated using quantitative low energy electron diffraction. The broken symmetry at the surface enhances the structural instability against the RuO6 rotational distortion while diminishing the instability against the RuO6 tilt distortion occurring within the bulk crystal. As a result, suppressed structural and electronic surface phase transition temperatures are observed, including the appearance of an inherent Mott metal-to-insulator transition for x=0.1 and possible modifications of the surface quantum critical point near x(c) approximately 0.5.     

Quasi-two-dimensional mott transition system Ca2-xSrxRuO4

We have revealed the phase diagram of Ca2-xSrxRuO4: the quasi-two-dimensional Mott transition system that connects the Mott insulator Ca2RuO4 with the spin-triplet superconductor Sr2RuO4. Adjacent to the metal/nonmetal transition at x approximately 0.2, we found an antiferromagnetically correlated metallic region where non-Fermi-liquid behavior in resistivity is observed. Besides this, the critical enhancement of susceptibility toward the region boundary at x(c) approximately 0.5 suggests the crossover of magnetic correlation to a nearly ferromagnetic state, which evolves into the spin-triplet superconductor Sr2RuO4.     

Fragile magnetic ground state in half-doped LaSr2Mn2O7

We investigated the orbital and antiferromagnetic ordering behaviors of the half-doped bilayer manganite La(2-2x)Sr(1+2x)Mn2O7 (x ? 0.5) by using Mn L(2,3)-edge resonant soft x-ray scattering. Resonant soft x-ray scattering reveals the CE-type orbital order below T(oo) ? 220 K, which shows partial melting behavior below T(m) ? 165 K. We also found coexistence CE- and A-type antiferromagnetic orders. Both orders involve the CE-type orbital order with nearly the same orbital character and are coupled with each other. These results manifest that the ground state with the CE-type antiferromagnetic order is easily susceptible to destabilization into the A-type one even with a small fluctuation of the doping level, as suggested by the extremely narrow magnetic phase boundaries at x ? 0.5±0.005.     

Anomalous spin-density distribution on oxygen and Ru in Ca(1.5)Sr(0.5)RuO(4): polarized neutron diffraction study

By means of polarized neutron diffraction in a magnetic field of 7.0 T at 1.6 K an anomalously large magnetization density is observed on the in-plane oxygen in Ca(1.5)Sr(0.5)RuO(4). Field-induced moments of different ions are determined by refinement on the flipping ratios, yielding micro(Ru)=0.346(11)micro(B), micro(O1)=0.076(6)micro(B), and micro(O2)=0.009(6)micro(B). The moment on the oxygen arises from the strong hybridization between the Ru-4d and O-2p orbitals. The maximum entropy magnetization density reconstruction reveals a strongly anisotropic density at the Ru site, consistent with the distribution of the xy (t(2g) band) d orbitals.     

Orbital-ordering transition in Sr2VO4

Temperature-dependent dc susceptibility and x-ray powder diffraction on a pure tetragonal sample of Sr(2)VO(4) show an antiferromagnetic orbital-ordering transition at T(oo) = 97 K, in which the occupied orbitals lie along the c axis. The unusual broadening of the x-ray Bragg peaks throughout the orbital-ordering transition temperature region indicates that this process occurs in stages, and the onset of short-range orbital ordering occurs at T(1) approximately 122 K. The study of the order parameter associated with this transition by analyzing the spontaneous strain results in a critical exponent beta = 0.35(2) consistent with 3D Heisenberg behavior. These results experimentally confirm the orbital-ordering state in Sr(2)VO(4) predicted by first-principles calculations using combinations of the local-density approximation and the GW method.     

Neutron powder diffraction investigation on the crystal and magnetic structure of (Ho(0.50+x)Ca(0.50-x))(Mn(1-x)Cr(x))O3

The crystal and magnetic structure of (Ho(0.50+x)Ca(0.50-x))(Mn(1-x)Cr(x))O(3) (x = 0.00, 0.01, 0.02, 0.03) has been investigated between 5 and 300 K by means of neutron powder diffraction followed by Rietveld refinement and dc magnetic measurements. During cooling an orthorhombic to monoclinic phase transition occurs on account of the charge and orbital ordering taking place in the Mn sub-lattice; at low temperature phase separation takes place and the main monoclinic phase coexists with a secondary orthorhombic phase, whose amount slightly increases with the increase of Cr content. Cr(3+) is not involved in orbital ordering or superexchange interactions. The charge and magnetic ordering are decoupled: the Mn moments order according to a CE-type structure in all samples.     

Heavy-mass fermi liquid near a ferromagnetic instability in layered ruthenates

Low temperature magnetic, thermal, and transport measurements in Ca2-xSrxRuO4 clarify the appearance of a cluster glass phase, after the evolution of a nearly ferromagnetic heavy-mass Fermi liquid from the spin-triplet superconductor Sr2RuO4. As the Mott transition is approached across a 2nd-order structural transition, both the magnetization and specific heat decrease considerably while the transport scattering rate diverges. A metamagnetic transition to a highly spin polarized state, with a local moment S=1/2, is observed. We argue that an orbital rearrangement with Ca substitution changes itinerant ferromagnetism to antiferromagnetism of localized moments.     

Field-induced paramagnons at the metamagnetic transition of Ca1.8Sr0.2RuO4

The magnetic excitations in Ca1.8Sr0.2RuO4 were studied across the metamagnetic transition and as a function of temperature using inelastic neutron scattering. At low temperature and low magnetic field the magnetic response is dominated by a complex superposition of incommensurate antiferromagnetic fluctuations. Upon increasing the magnetic field across the metamagnetic transition, paramagnon and finally well-defined magnon scattering is induced, partially suppressing the incommensurate signals. The high-field phase in Ca1.8Sr0.2RuO4, therefore, has to be considered as an intrinsically ferromagnetic state stabilized by the magnetic field.     

Low to high spin-state transition induced by charge ordering in antiferromagnetic YBaCo2O5

The oxygen-deficient double perovskite YBaCo2O5, containing corner-linked CoO5 square pyramids as principal building units, undergoes a paramagnetic to antiferromagnetic spin ordering at 330 K. This is accompanied by a tetragonal to orthorhombic distortion. Below 220 K orbital ordering and long-range Co(2+)/Co(3+) charge ordering occur as well as a change in the Co2+ spin state from low to high spin. This transition is shown to be very sensitive to the oxygen content of the sample. To our knowledge this is the first observation of a spin-state transition induced by long-range orbital and charge ordering.