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.     

Mott transition and suppression of orbital fluctuations in orthorhombic 3d1 perovskites

Using t(2g) Wannier functions, a low-energy Hamiltonian is derived for orthorhombic 3d(1) transition-metal oxides. Electronic correlations are treated with a new implementation of dynamical mean-field theory for noncubic systems. Good agreement with photoemission data is obtained. The interplay of correlation effects and cation covalency (GdFeO3-type distortions) is found to suppress orbital fluctuations in LaTiO3 and even more in YTiO3, and to favor the transition to the insulating state.     

Orbital ordering in e(g) orbital systems: ground states and thermodynamics of the 120° model

Orbital degrees of freedom shape many of the properties of a wide class of Mott insulating, transition metal oxides with partially filled 3d shells. Here we study orbital ordering transitions in systems where a single electron occupies the e(g) orbital doublet and the spatially highly anisotropic orbital interactions can be captured by an orbital-only model, often called the 120° model. Our analysis of both the classical and quantum limits of this model in an extended parameter space shows that the 120° model is in close proximity to several T=0 phase transitions and various competing ordered phases. We characterize the orbital order of these nearby phases and their associated thermal phase transitions by extensive numerical simulations and perturbative arguments.     

Dynamics of orbital degree of freedom in transition-metal oxides

The collective excitation in the orbital degree of freedom termed orbital wave is studied in the orbital ordered transition-metal oxides, in particular, in LaMnO₃. Symmetry, dispersion and energy gap of this excitation are examined by the group theoretical analyses and the linear spin-wave theory. The cross-section of the Raman scattering from the orbital wave is calculated and is compared with the recent experimental results.     

Electronic structures of the LaBO3 (B = Co, Fe, Al) perovskite oxides related to their catalysis

The discrete-variational (DV) X α molecular orbital method has been applied to investigate the bulk and surface electronic structures of perovskite oxides such as LaCoO₃, LaFeO₃ and LaAlO₃. The calculated XPS spectra for these oxides are in good agreement with the experimental ones and only the LaCoO₂ exhibited a rather high electron density of states near the Fermi level (E_F). The catalytic behavior of these oxides is discussed on the basis of their electronic structures; the marked catalysis by LaCoO₃ is associated with electron occupation of crystal field d states near E_F and with the buildup of surface charge so as to enhance the electron transfer between a surface cation and an interacting molecule.     

The shape and extended fine structure of the manganese K X-ray absorption discontinuity in its oxides

The shape and extended fine structure of the manganese K absorption discontinuity have been studied in the pure metal and in its four oxides. viz. MnO, Mn₃O₄, Mn₂O₃ ad MnO₂ using a bent crystal Cauchois type spectrograph of 40cm diameter. The shape of the main discontinuity for the oxides is discussed on the basis of molecular orbital theory. Our results show a complimentarity between the absorption spectra and the emission spectra obtained earlier by Tsutsumi et al. for some of these oxides. The extended X-ray absorption fine structure (EXAFS) is discussed in the light of the recent proposed by Lytle et al.     

The electronic structures of the core and valence ion states of metal oxides

SCF-Xα SW MO calculations on metal core ion hole states and X-ray emission (XES) and X-ray photoelectron (XPS) transition states of the non- transition metal oxidic clusters MgO₆^10?, AlO₄^5? and SiO₄^4? show relative valence orbital energies to be virtually unaffected by the creation of valence orbital or metal core orbital holes. Accordingly, valence orbital energies derived from XPS and XES are directly comparable and may be correlated to generate empirical MO diagrams. In addition, charge relaxation about the metal core hole is small and valence orbital compositions are little changed in the core hole state. On the other hand, for the transition metal oxidic clusters FeO₆^10?, CrO₆^9? and TiO₆^8? relative valence orbital energies are sharply changed by a metal core orbital or crystal field orbital hole, the energy lowering of an orbital increasing with its degree of metal character. Consequently O 2p nonbonding → M 3d-O 2p antibonding (crystal field) energies are reduced, while M 3d bonding → O 2p nonbonding and M 3d-O 2p antibonding → M 4s,p-O 2p antibonding (conduction band) energies increase. Charge relaxation about the core hole is virtually complete in the transition metal oxides and substantial changes are observed in the composition of those valence orbitals with appreciable M 3d character. This change in composition is greater for e _g than for t_2g orbitals and increases as the separation of the e_g crystal field (CF) orbitals and the O 2p nonbonding orbital set decreases. Based on the hole state MO diagrams the higher energy XPS satellite in TiO₂ (at about 13 eV) is assigned to a valence → conduction band transition. The UV PES satellites at 8.2 eV in Cr₂O₃ and 9.3 eV in FeO are tentatively assigned to similar transitions to conduction band orbitals, although the closeness in energy of the crystal field and O 2p nonbonding orbitals in the valence orbital hole state prevents a definite assignment on energy criteria alone. However the calculations do clearly show that charge transfer transitions of the e_g bonding → e_g crystal field orbital type would generally occur at lower energy than is consistent with observed satellite structure.A core electron hole has little effect upon relative orbital energies and is only slightly neutralized by valence electron redistribution for MgO and SiO₂. For the transition metal oxides a core hole lowers the relative energies of M3d containing orbitals by large amounts, reducing O → M charge transfer and increasing M 3d crystal field → conduction band energies. Large and sometimes overcomplete neutralization of the core hole is observed, increasing from CrO₆^9? to FeO₆^10? to TiO₆^8?. as the O → M charge transfer energy declines.High energy XPS satellites in TiO₂ may be assigned to O 2p nonbonding → conduction band transitions while lower energy UV PES satellites in FeO and Cr₂O₃ arise from crystal field or O 2p nonbonding → conduction band excitations. Our “shake-up” assignment for FeO₆^10?, CrO₆^9? and TiO₆^8? are less than definitive because no procedure has yet been developed to calculate “shake-up” intensities resulting from transitions of the type described. However the results do allow a critical evaluation of earlier qualitative predictions of core and valence hole effects. First, we find that the comparison of hole or valence state ionic systems with equilibrium distance systems of higher nuclear and/or cation charge (e.g. the comparison of the FeO₆^10? Fe 2p core hole state to Co₃O₄) is dangerous. For example, larger MO distances in the ion states substantially reduce crystal field splittings. Second, core and CF orbital holes sharply reduce O → M charge transfer energies, giving 2e_g → 3e_g energy separations which are generally too small to match observed satellite energies. Third, highest occupied CF-conduction band energies are only about 4–5 eV in the ground states, but increase to about 7–11 eV in the core and valence hole states of the transition metal oxides studied. The energetic arguments presented thus support the idea of CF and/or O 2p nonbonding → conduction band excitations as assignments for “shake-up” satellites, at least in oxides of metals near the beginning of the transition series.     

Raman scattering in the Mott insulators LaTiO3 and YTiO3: evidence for orbital excitations

Raman scattering is used to observe pronounced electronic excitations around 230 meV--well above the two-phonon range--in the Mott insulators LaTiO3 and YTiO3. Based on the temperature, polarization, and photon energy dependence, the modes are identified as orbital excitations. The observed profiles bear a striking resemblance to magnetic Raman modes in the insulating parent compounds of the superconducting cuprates, indicating an unanticipated universality of the electronic excitations in transition metal oxides.     

Dynamical mean-field theory of nickelate superlattices

Dynamical mean-field methods are used to calculate the phase diagram, many-body density of states, relative orbital occupancy, and Fermi-surface shape for a realistic model of LaNiO(3)-based superlattices. The model is derived from density-functional band calculations and includes oxygen orbitals. The combination of the on-site Hunds interaction and charge transfer between the transition metal and the oxygen orbitals is found to reduce the orbital polarization far below the levels predicted either by band-structure calculations or by many-body analyses of Hubbard-type models which do not explicitly include the oxygen orbitals. The findings indicate that heterostructuring is unlikely to produce one band-model physics and demonstrate the fundamental inadequacy of modeling the physics of late transition-metal oxides with Hubbard-like models.     

Rh2O3 versus IrO2: relativistic effects and the stability of Ir4+

Despite the wide-ranging applications of binary Rh and Ir oxides, their stability and trends in Rh and Ir oxidation states are not fully understood. Using first-principles electronic structure calculations, we demonstrate that the origin of the categorical stability of Ir(4+) is the relativistic contraction of the 6s orbital and, consequently, an expansion of 5d orbitals. Relativistic effects significantly stabilize Ir(4+)-containing metallic rutile IrO(2) over a wide range of O chemical potentials, despite the choice that Ir has of forming semiconducting corundum Ir(2)O(3). In contrast, Rh is found to display a wider stability range for corundum Rh(2)O(3) with Rh(3+) and a greater propensity for multiple oxidation states.     

Electrical control of magnetism in oxides

Recent progress in the electrical control of magnetism in oxides,with profound physics and enormous potential applications,is reviewed and illustrated.In the first part,we provide a comprehensive summary of the electrical control of magnetism in the classic multiferroic heterostructures and clarify the various mechanisms lying behind them.The second part focuses on the novel technique of electric double layer gating for driving a significant electronic phase transition in magnetic oxides by a small voltage.In the third part,electric field applied on ordinary dielectric oxide is used to control the magnetic phenomenon originating from charge transfer and orbital reconstruction at the interface between dissimilar correlated oxides.At the end,we analyze the challenges in electrical control of magnetism in oxides,both the mechanisms and practical applications,which will inspire more in-depth research and advance the development in this field.     

The electronic structure of alkali metal oxides

Crystalline phase total energies, band structures, the distributions of the total and partial densities of electron states, and atomic charges were calculated for lithium, sodium, and potassium oxides, peroxides, superoxides, and ozonides using the CRYSTAL 06 and GAMESS packages in the B3LYP parameterization. For the molecular phases, the geometry was optimized and molecular orbital energies calculated. The results obtained for metal oxides were compared with the experimental photoelectron spectroscopy data and used to analyze their formation and thermal decomposition.     

A molecular orbital model for the electronic structure of transition metal atoms in silcate and aluminate alloys

Applied to transition metal oxides and silicate and aluminate alloys, a classification scheme that separates non-crystalline dielectrics into three groups with different amorphous morphologies, demonstrates a direct correlation between stability against crystallization and oxygen atom coordination. It also provides a local bonding model for molecular orbital (MO), calculations that are based on the coordination and symmetry of transition metal atoms and the orbital energies of their oxygen neighbors. These calculations provide important insights into the electronic structure of transition metal dielectrics, e.g. the role of anti-bonding d-states in determining conduction band offset energies with respect to Si.     

Electronic excitations in hole-doped La1−xSrxMnO3 studied by resonant inelastic X-ray scattering

We report a resonant inelastic X-ray scattering (RIXS) study on perovskite manganese oxides La_1−xSr_xMnO₃ (x=0, 0.2, and 0.4) at Mn K-absorption edge. Hole-doping effect on the electronic excitations in the strongly correlated electron systems is elucidated by comparing with undoped LaMnO₃. The scattering spectra of metallic La_0.6Sr_0.4MnO₃ show that a salient peak appears in low energies indicating the persistence of the Mott gap. At the same time, the energy gap is partly filled by doping holes and the spectral weight shifts toward lower energies. Though the peak position of the excitations shows weak dispersion in momentum dependence, RIXS intensity changes as a function of the scattering angle (2θ), which is related to the anisotropy. Furthermore, anisotropic temperature dependence is observed in La_0.8Sr_0.2MnO₃ which shows a metal-insulator transition associated with a ferromagnetic transition. We consider that the anisotropy in the RIXS spectra is possibly attributed to the correlation of the orbital degrees of freedom. The anisotropy is large in LaMnO₃ with long-range orbital order, while it is small but finite in hole-doped La_1−xSr_xMnO₃ which indicates persistence of short-range orbital correlation.     

The electronic structures of Mg,Al and Si in octahedral coordination with oxygen from SCF Xα MO calculations

Molecular orbital calculations performed using the SCF Xα Scattered Wave Cluster method are presented for the octahedral oxyanions MgO₆^?10, AlO₆^?9 and SiO₆^?8. The AlO₆^?9 results are used to assign and interpret the X-ray photoelectron spectra (XPS), X-ray emission (XES) and u.v. spectra of Al₂O₃. Agreement between calculation and experiment is good for valence band and fair for conduction band orbitais. The SCF Xα results for MgO₆^?10 are also in good agreement with observed valence band energies in MgO, but in this case the lowest energy features in the u.v. spectrum are not assignable in terms of either the calculations or the X-ray spectral results. The substantial increase in covalency expected between the Mg and Si oxides is evidenced in the calculations by an increase in valence region width from 2.6 to 5.3 eV and an increase in valence-conduction band separation from 5.2 to 10.0 eV. The calculated trends are in reasonable agreement with u.v. spectral data and with absolute valence orbital binding energies derived from X-ray spectra. A comparison of the SiO₆^?8 calculation with the analogous tetrahedral SiO₄^?4 calculation shows the valence band in the octahedral oxyanion to be much simpler in structure and somewhat narrower than that in the tetrahedral oxyanion. Using the orbital structure calculated for the valence bands of tetrahedral and octahedral oxides, a method is presented for calculating atomization energies directly from X-ray spectral data for SiO₂, Al₂O₃ and MgO. Results are in good agreement with experiment but the method involves an empirical parameter which is not presently understood in detail. Studies of trends in p-type bonding orbital binding energies derived from experimental data provide a qualitative explanation for the preferred coordination numbers in the Mg, Al and Si oxides.     

Oxygen K-edge in vanadium oxides: simulations and experiments

Band-structure (BS) calculations of the density of states (DOS) using the full potential augmented plane waves code WIEN97 were performed on the four single-valence vanadium oxides VO, V₂O₃, VO₂ and V₂O₅. The DOS are discussed with respect to the distortions of the VO₆ octahedra, the oxidation states of vanadium and the orbital hybridisations of oxygen atoms. The simulated oxygen K-edge fine structures (ELNES) calculated with the TELNES program were compared with experimental results obtained by electron energy-loss spectrometry (EELS), showing good agreement. We show that changes in the fine structures of the investigated vanadium oxides mainly result from changes in the O-p DOS and not from the shift of the DOS according to a rigid band model. Received 17 December 2001 / Received in final form 19 June 2002 Published online 13 August 2002     

Directional ordering of fluctuations in a two-dimensional compass model

In the Mott insulating phase of the transition metal oxides, the effective orbital-orbital interaction is directional both in orbital space and in real space. We discuss a classical realization of directional coupling in two dimensions. Despite extensive degeneracy of the ground state, the model exhibits partial orbital ordering in the form of directional ordering of fluctuations at low temperatures stabilized by an entropy gap. Transition to the disordered phase is shown to be in the Ising universality class through exact mapping and multicanonical Monte Carlo simulations.     

Transition states in Ei reactions

The pyrolysis of amine oxides, sulfoxides, selenoxides, and esters to form alkenes is believed to be a concerted reaction with a cyclic transition state. Phosphine oxides, sulfones, and nitro compounds are unreactive. This study seeks to identify reasons for the lack of reactivity of the latter. Transition states were located for all substrates progressing from RHF/3‐21G* to the MP2/6‐31+G(d,p) level (in certain cases). For sulfones and nitro compounds, two possible reasons for lack of reactivity were considered: (1) Atoms approaching one another in the transition state may be considered to participate in a local n_O → σ*_CH interaction. The second oxygen in the sulfone or nitro compound lowers the energy of the ‘non‐bonded electrons’ at oxygen leading to a greater mismatch in energy with the antibonding C? H orbital (in comparison to the sulfoxide or amine oxide). (2) The sulfone and nitro ‘lone pairs’ are not really ‘alone’, and available to react. In fact, complex bonding arrangements exist in the SO₂ and NO₂ groups. The situation is less clear for phosphine oxides, although ground state stability of bonds is important. Implications concerning the Hammond postulate are covered. Copyright © 2009 John Wiley & Sons, Ltd.     

层状氧化钼的电子结构、磁和光学性质第一原理研究

按照基于自旋密度泛函理论的赝势平面波第一原理计算方法,理论研究了两种层堆叠结构氧化钼(正交和单斜MoO_3)的电子结构、磁性和光学特性,探讨其作为电致变色材料或电磁材料在光电子器件中的技术应用.采用先进的半局域GGA-PW91和非局域HSE06交换相关泛函精确计算晶体结构和带隙宽度.计算得出较低密排面解离能,表明两种层状氧化钼的单片层很容易从体材料上剥落.能带结构和投影态密度分析表明:导带底和价带顶电子态主要来自于层平面方向成键的原子轨道,呈现典型的二维电子结构特征.无缺陷的MoO_3块体材料具有明显的磁矩,O空位会导致磁矩增加;由Mo原子和顶点氧原子产生的亚铁磁耦合磁矩是MoO_3层状材料磁性的主要来源;层状氧化钼在可见光区具有明显的光吸收响应,光吸收谱表现出显著的各向异性并在带电时发生明显的蓝移或形成新的低频可见光吸收峰.计算结果证明层状氧化钼具有明显的电致变色和磁控性能,为设计高性能电磁或光电子功能材料提供了理论依据和技术数据.