Dynamical disorder of spin-induced Jahn-Teller orbitals with the insulator-metal transition in cobaltites

Using elastic and inelastic neutron scattering, we investigated the evolution of the local atomic structure and lattice dynamics of La(1-x)SrxCoO3 (x=0-0.5) as it crosses over with x from an insulator to a ferromagnetic metal (FMM). Our pair density function analysis indicates that, in the paramagnetic insulating phase for all x, spin activation of Co3+ ions induces local static Jahn-Teller (JT) distortions. The size of the JT lattice increases almost linearly with x. However, in the FMM phase, static JT distortions are absent for x< or =30%. This coincides with narrowing of variant Planck's constant over 2 pi omega=22 and 24 meV modes in the phonon spectrum which we argue is due to localized dynamical JT fluctuations. For x>30%, static JT distortions reappear along with broadening of the phonon modes because of weakened charge-lattice interactions.     

Cooperative Jahn-Teller phase transition in LaMnO3 studied by X-ray absorption spectroscopy

The local structure of LaMnO3 across the Jahn-Teller (JT) transition at T(JT)=750 K was studied by means of x-ray absorption near edge structure and extended x-ray absorption fine structure at the Mn K-edge. Our results indicate a similar electronic local structure for Mn atoms above and below T(JT) and a dynamical tetragonal JT distortion of MnO6 octahedra above T(JT). The structural transition is originated by the ordering of tetragonally distorted octahedra. The entropy content of the transition is analyzed within the framework of the three-state Potts model with nearest neighbor antiferrodistortive coupling.     

The effect of band Jahn-Teller distortion on the magnetoresistivity of manganites: a model study

We present a model study of magnetoresistance through the interplay of magnetisation, structural distortion and external magnetic field for the manganite systems. The manganite system is described by the Hamiltonian which consists of the s-d type double exchange interaction, Heisenberg spin-spin interaction among the core electrons, and the static and dynamic band Jahn-Teller (JT) interaction in the e(g) band. The relaxation time of the e(g) electron is found from the imaginary part of the Green's function using the total Hamiltonian consisting of the interactions due to the electron and phonon. The calculated resistivity exhibits a peak in the pure JT distorted insulating phase separating the low temperature metallic ferromagnetic phase and the high temperature paramagnetic phase. The resistivity is suppressed with the increase of the external magnetic field. The e(g) electron band splitting and its effect on magnetoresistivity is reported here.     

Pressure-induced quenching of the Jahn-Teller distortion and insulator-to-metal transition in LaMnO(3)

LaMnO(3) was studied by synchrotron x-ray diffraction, optical spectroscopies, and transport measurements under pressures up to 40 GPa. The cooperative Jahn-Teller (JT) distortion is continuously reduced with increasing pressure. There is strong indication that the JT effect and the concomitant orbital order are completely suppressed above 18 GPa. The system, however, retains its insulating state to approximately 32 GPa, where it undergoes a bandwidth-driven insulator-metal transition. Delocalization of electron states, which suppresses the JT effect but is insufficient to make the system metallic, appears to be a key feature of LaMnO(3) at 20-30 GPa.     

Anomalous high-pressure Jahn-Teller behavior in CuWO4

High-pressure optical-absorption measurements performed in CuWO(4) up to 20 GPa provide experimental evidence of the persistence of the Jahn-Teller (JT) distortion in the whole pressure range both in the low-pressure triclinic and in the high-pressure monoclinic phase. The electron-lattice couplings associated with the e(g)(E?e) and t(2g)(T?e) orbitals of Cu(2+) in CuWO(4) are obtained from correlations between the JT distortion of the CuO(6) octahedron and the associated structure of Cu(2+) d-electronic levels. This distortion and its associated JT energy (E(JT)) decrease upon compression in both phases. However, both the distortion and associated E(JT) increase sharply at the phase-transition pressure (P(PT)=9.9 GPa), and we estimate that the JT distortion persists for a wide pressure range not being suppressed up to 37 GPa. These results shed light on the transition mechanism of multiferroic CuWO(4), suggesting that the pressure-induced structural phase transition is a way to minimize the distortive effects associated with the toughness of the JT distortion.     

Percolation features of cooperative Jahn-Teller systems: Ising EFT framework

Elastic exchange between two nearest Jahn-Teller (JT) centers in two or three dimensional dense crystals, can give an ordered macroscopic distortion known as cooperative JT effect (CJTE). A very diluted JT crystal does not show this effect. In the dynamic JT effect (DJTE), tunneling between different equivalent distorted wells has a pronounced influence on the CJTE. We investigate this phenomenon using a progressive increase in the concentration of these centers in the JT crystals, based on a bond percolation vector spin analogy technique within the framework of effective field theory (EFT). Mean field theory (MFT) was extensively used in previous studies of CJTE; however it neither includes correlation between JT centers in the lattice due to the complexity of the distortion field in the crystal nor the effect of tunneling between wells. We resort to an alternative procedure, by describing a JT center as a pseudo-spin vector \(\vec S\), induced to represent the degenerate JT-distorted states, where two nearest JT centers interact via an elastic exchange described by an Ising type spin interaction. The DJTE is considered to be similar to an elastic transverse field term in the Hamiltonian portraying the effect of tunneling between equivalent wells in the adiabatic potential energy surface (APES). We will be particularly discussing S = 1, S = 3/2 and S = 5/2 spin cases, where 2S + 1 wells in the APES are present and what JT systems they actually represent, with a percolative mechanism applied to the interactions between different JT centers. The different lattices are distinguished by their coordination numbers. Strong tunneling effects can suppress the CJTE and lead to a new state of criticality. Generalizations to higher spin systems will be obtained using a scaling technique. For the relevant distortions, we determine single site correlations, the macroscopic average distortion describing a structural phase transition and the elastic isothermal susceptibility as a function of temperature. The critical bond percolation threshold and the critical tunneling parameter are also obtained.     

Raman study of the orbital-phonon coupling in LaCoO3

The magnetic state in LaCoO3 changes from the low spin state (S=0) to the mixed state with a thermally excited intermediate spin state (IS) (S=1) above about 50 K. The partially filled e(g) orbital in the IS state has a nature of Jahn-Teller (JT) distortion. The cooperative JT distortion causes an orbital order. We found that all Raman active phonon modes are affected by the excitation of IS Co3+ ions. Especially, the JT vibration mode shows anomalous temperature dependence.     

Unexpected behavior of the local compressibility near the B = 0 metal-insulator transition

We have measured the local electronic compressibility of a two-dimensional hole gas as it crosses the B = 0 metal-insulator transition. In the metallic phase, the compressibility follows the mean-field Hartree-Fock (HF) theory and is found to be spatially homogeneous. In the insulating phase it deviates by more than an order of magnitude from the HF predictions and is spatially inhomogeneous. The crossover density between the two types of behavior agrees quantitatively with the transport critical density, suggesting that the system undergoes a thermodynamic change at the transition.     

Structural distortion in the primitive cubic phase of the superconducting/magnetic ternary rare-earth rhodium stannides

A structural distortion in the primitive cubic phase of the SnM₃Rh₄Sn₁₂ compounds with M = La, Ce, Pr, Nd, Sm, and Gd has been detected by electron diffraction and studied by X-ray diffraction. On the contrary, no distortion has been detected for the compounds with M = Eu, Yb, Ca, Sr, and Th. The La, Yb, Ca, Sr, and Th compounds become superconductors with T_c ranging between 8.7 K and 1.9 K, whereas those of Eu and Gd have a magnetic transition at about 11 K. Long exposure (200 hrs.) precession photographs revealed the existence of superstructure spots which can be indexed either on a body-centered cubic cell with a_I = 2a_cp or on a tetragonal cell with a_T = ∫2 a_cp and c_T = c_cp. In this latter case the sample must be considered as twinned and the extra spots would come from three different individuals each having the tetragonal axis along one of the three cubic fourfold axes. However, electron microscope photographs have failed so far to reveal the existence of domains. From the systematic absences it has been determined that the cubic distortion belongs to space group I2₁3 while the tetragonal one to space group P4₂22. The main effect of the distortion is the lowering of the site symmetries which favors the disorder between the cationic tin and the M atoms. The size of these latter atoms does not seem to be an important factor for the distortion. The only feature which separates the distorted compounds from the undistorted ones is the valence of the M atoms. However, no explanation can be offered why the valence plays an important role for the distortion.     

Pressure-induced closure of the jahn-teller distortion in Rb2CuCl4(H2O)2

This work investigates the pressure-induced variation of the local structure around Cu²⁺ as well as the crystal structure in Rb₂CuCl₄(H₂O)₂ through XAS and XRD techniques. The application of pressure induces a structural change in the Jahn-Teller (JT) [Formula: See Text] complex from axially elongated to compressed. This change leads to the closing of the 2D JT distortion related to the four in-plane Cl^? ligands, which are responsible for the antiferrodistortive structure displayed by the crystal. It is shown that the presence of water ligands enhances a JT release. Their associated axial ligand-field favours the occurrence of such a local structural transition below the metallization pressure. The results are compared with recent pressure experiments on A₂CuCl₄ systems.     

Structural changes in RNiO3 perovskites (R=rare earth) across the metal–insulator transition

Rare earth nickel oxide perovskites (RNiO₃, R=rare earth) have, except for LaNiO₃, a metal–insulator (MI) phase transition as temperature decreases. The transition temperature (T_MI) increases as the R-ion becomes smaller. They also present, at low temperatures, a complex antiferromagnetic order. For lighter R-ions (e.g. Pr and Nd), the antiferromagnetic transition temperature (T_N) is close to T_MI, while for heavier R-ions (e.g. Eu, Sm), T_MI and T_N are very far apart, suggesting that the magnetic and electronic behaviors are not directly coupled. Even though Ni³⁺ is a Jahn–Teller ion, no distortion in the NiO₆ octahedra was found for RNiO₃ perovskites with R=Pr, Nd, Sm and Eu. In this work we have measured EXAFS at Ni K edge for samples of PrNiO₃, NdNiO₃ and EuNiO₃. The Fourier transform spectra for the three samples show a clear splitting in the first peak at the insulating phase. This splitting corresponds to two or more different Ni–O distances. This indicates that there is either a distortion in the NiO₆ octahedra or there are two different Ni sites at the insulating phase.     

Ferro-type orbital state in the Mott transition system Ca2-xSrxRuO4 studied by the resonant x-ray scattering interference technique

We have succeeded in detecting ferro-type orbital states in Ca2-xSrxRuO4, which is the first outcome in a 4d Mott transition system by the resonant x-ray scattering interference technique. For x=0 (Mott insulator), the resonant signal for d(xy) orbital ordering is observed even at room temperature, in which the Jahn-Teller distortion is negligible. The signal disappears near the metal-insulator transition. On the other hand, in a metallic phase for x=0.5, orbital polarization with d(yz/zx) character dominates. With lowering temperature, the magnitude of the resonant signal slightly decreases owing to the additional influence of the gamma band with d(xy) character.     

Pseudogap behavior in Pr0.5Sr0.5MnO3: A photoemission study

The valence band electronic structure of Pr_0.5Sr_0.5MnO₃ has been investigated across its paramagnetic metallic (PMM)–ferromagnetic metallic (FMM)–antiferromagnetic insulator (AFMI) transition. Using surface sensitive high resolution photoemission we have conclusively demonstrated the presence of a pseudogap of magnitude 80 meV in the near Fermi level electronic spectrum in the PMM and FMM phases and finite intensity at the Fermi level in the charge ordering (CO)-AFMI phase. The pseudogap behavior is explained in terms of the strong electron–phonon interaction and the formation of Jahn Teller (JT) polarons, indicating the charge localizations. The finite intensity at the Fermi level in the insulating phase showed a lack of charge ordering in the surface of the Pr_0.5Sr_0.5MnO₃ samples.     

On the pressure-temperature phase diagram of intermediate valence compounds

The pressure-temperature (P, T) phase diagram of intermediate valence compounds has been calculated on the basis of the periodic Anderson model which was extended to include the interaction of 4f electrons with longitudinal optical phonons. It is shown that the positive slope (dP/dT>0) of the phase boundary between the insulating and the mixed valence phase as observed experimentally in Sm S and many other systems is determined by the behaviour of the electronic density of states of the interacting system as function ofP. Moreover, the observed anomalous thermal contraction in the insulating phase near the phase boundary and the anomalously large thermal expansion in the metallic phase are well described by numerical results for the extended periodic Anderson model.     

55Mn NMR investigation of electronic phase separation in La1-xCaxMnO3 for 0.2 < or = x < or = 0.5

55Mn NMR line shape measurements in La1-xCaxMnO3 for 0.20< or =x< or =0.50 provide experimental evidence about the existence of two distinct regions in the T-x magnetic phase diagram, where the homogeneous ferromagnetic (FM) metallic state is separated into FM metallic and FM insulating regions. These results are in agreement with recent theoretical predictions, which reveal a novel electronic phase separation in two FM states, providing orbital ordering and Jahn-Teller phonons are taken into consideration.     

The influence of quantum fluctuations on quantum hall phases at large

We have explored the behavior of a two-dimensional hole system in the regime of very low densities and hence large r_s. The electronic phases at the largest magnetic fields have surprising behavior. We found that with decreasing density the reentrant insulating phase weakens until it completely disappears. We also found that at the collapse of the reentrant insulator the nearby fractional quantum Hall liquid is unexpectedly suppressed. Both of these properties can be understood as stemming from quantum fluctuations of the insulating electronic solid.     

Stress evolution and lattice distortion induced by thickness variation and lattice misfit in La0.67Sr0.33MnO3−δ films

La_0.67Sr_0.33MnO_3?δ thin films with different thicknesses are prepared in order to investigate the structural variation induced by film thickness and lattice misfit. The X-ray diffraction results show the in-built stress evolution from a full strained thin layer (～10 nm) to a completely relaxed thick layer (～150 nm), which can be well explained by the Poisson effect. Raman spectroscopy measurements reveal the complicated correlation between the Jahn–Teller (JT) distortion and film thickness. Important octahedron modes reflecting JT distortion are completely caused by the relaxed layer. It is observed that broad JT bands are formed in the films with large thickness of the relaxed layer and the residual stress in the layer leads to an obvious blue shift. In contrast, for films with the thin relaxed layer, JT modes are present as a sharper structure and move to low frequency, indicating towards a much better oxygen stoichiometry.     

Orbital-spin structure and lattice coupling in RTiO3 where R=La, Pr, Nd, and Sm

The origin of the G-type antiferromagnetism [AFM(G)] and puzzling properties of RTiO3 with R=La are studied. We clarify that the crystal field from La caused by the GdFeO3-type distortion lifts the t(2g) degeneracy at Ti 3d orbitals. The lift stabilizes the AFM(G) with spin-exchange constant in agreement with neutron-scattering results. The orbital-spin structures for R=Pr, Nd, and Sm are also consistent with experiments. We propose that the GdFeO3-type distortion has a universal mechanism of controlling orbital-spin structure competing with the Jahn-Teller (JT) mechanism.     

晶体相场法研究预变形对熔点附近六角相/正方相相变的影响

应用双模晶体相场模型计算二维相图,并模拟了在熔点附近预变形和保温温度对六角相晶界演化以及六角相/正方相相变的影响.研究发现:在相变初期,当预变形为零、保温温度离熔点很近时在晶界发生缺陷诱发预熔;增大预变形,变形与缺陷的交互作用在熔点附近诱发预熔;随着预变形的进一步增大,变形在畸变处同时诱发液相和正方相,且预变形越大、保温温度越接近熔点,液相生长越明显,反之正方相生长明显.持续保温使得畸变能释放,晶粒最终完全转变为平衡正方相.模拟结果表明:预变形六角相在熔点附近保温时,由于晶界固有缺陷和预变形双重作用使得原子无序度增加,从而在晶界或其他缺陷处产生液相,待能量释放后晶粒再转变成平衡正方相,进而延缓了六角相/正方相相变时间.     

Orbital correlations in the pseudocubic O and rhombohedral R phases of LaMnO3

The local and intermediate structure of stoichiometric LaMnO3 has been studied in the pseudocubic and rhombohedral phases at high temperatures (300-1150 K). Neutron powder diffraction data were collected and a combined Rietveld and high real space resolution atomic pair distribution function analysis was carried out. The nature of the Jahn-Teller (JT) transition around 750 K is confirmed to be orbital order to disorder. In the high-temperature orthorhombic (O) and rhombohedral (R) phases, the MnO6 octahedra are still fully distorted locally. More importantly, the intermediate structure suggests the presence of local ordered clusters of diameter approximately 16 A ( approximately 4 MnO6 octahedra) implying strong nearest-neighbor JT antiferrodistortive coupling. These clusters persist well above the JT transition temperature even into the high-temperature R phase.