Optical evidence of quantum rotor orbital excitations in orthorhombic manganites

In magnetic compounds with Jahn–Teller (JT) ions (such as Mn³⁺ or Cu²⁺), the ordering of the electron or hole orbitals is associated with cooperative lattice distortions. There the role of JT effect, although widely recognized, is still elusive in the ground state properties. Here we discovered that, in these materials, there exist excitations whose energy spectrum is described in terms of the total angular momentum eigenstates and is quantized as in quantum rotors found in JT centers. We observed features originating from these excitations in the optical spectra of a model compound LaMnO₃ using ellipsometry technique. They appear clearly as narrow sidebands accompanying the electron transition between the JT split orbitals at neighboring Mn³⁺ ions, displaying anomalous temperature behavior around the Néel temperature T_N ≈ 140 K. We present these results together with new experimental data on photoluminescence found in LaMnO₃, which lend additional support to the ellipsometry implying the electronic-vibrational origin of the quantum rotor orbital excitations. We note that the discovered orbital excitations of quantum rotors may play an important role in many unusual properties observed in these materials upon doping, such as high-temperature superconductivity and colossal magnetoresistance.     

A DISCRETE VARIATIONAL METHOD STUDY ON THE ELECTRONIC STRUCTURES OF CaMnO3 AND LaMnO3

The electronic structures of the perovskite oxides, LaMnO₃ and CaMnO₃, with various magnetic structures are studied using the first-principles discrete variational (DV) cluster method based on ab initio local-spin-density approximation (LSDA). The ground states of different magnetic phases (including ferromagnetic (FM), A-type antiferromagnetic (A-AFM), and G-type antiferromagnetic (G-AFM)) have been described in this work. The cubic CaMnO₃ with observed G-AFM magnetic order is found to have a 0.1 eV calculated gap. Both FM CaMnO₃ and LaMnO₃ have "half-metallic" character, which is in agreement with other works. LaMnO₃ with both A-type and G-type antiferromagnetic order have metallic band structures. Part of Jahn-Teller (JT) distortion (Q₂ type) has been taken into consideration for A-AFM LaMnO₃. Under Q₂ type JT distortion, the occupied and unoccupied states of O 2p and Mn 3d states move farther away from the Fermi energy. It is also found that the distortion can further stabilize the structure. The density of states and the binding energy of the distorted A-AFM LaMnO₃ are given in this paper.     

Strain induced phase separation on La0.5Ca0.5MnO3 thin films

The effect of epitaxial strain on La_0.5Ca_0.5MnO₃ films of various thicknesses grown on SrTiO₃, SrLaAlO₄, and SrLaGaO₄ substrates is studied by Raman spectroscopy, magnetic, and resistivity measurements. The transport and magnetic properties as well as Raman spectra of the films are affected by epitaxial strains. The energy of the A_g(2) mode and the tilting angle of the MnO₆ octahedra is affected by the strain imposed by the substrate. In the spectra of the films deposited on the (1 0 0) SrTiO₃ substrate strong Jahn-Teller (JT) modes appear, which couple with charge-ordering. In all other films these modes are suppressed and no additional Raman lines are present at low temperatures contrary to the bulk compound. The low frequency continuum scattering decreases at low temperatures indicating a coupling with both the charge and orbital transitions. Comparison of the Raman spectra with the magneto-transport properties suggests an interpretation in terms of a strain induced phase separation between ferromagnetic metallic and antiferromagnetic insulating states.     

Lattice relaxation and charge-transfer optical transitions due to self-trapped holes in nonstoichiometric LaMnO3 crystal

We explore the role of electronic and ionic polarization energies in the physics of “colossal” magnetoresistive (CMR) materials. We use the Mott-Littleton approach to evaluate polarization energies in the LaMnO₃ lattice associated with holes localized on both the Mn³⁺ cation and the O^2?anion. The full (electronic and ionic) lattice relaxation energy for a hole localized at the O site is estimated at 2.4 eV, which is appreciably greater than that of 0.8 eV for a hole localized at the Mn site, indicating a strong electron-phonon interaction in the former case. The ionic relaxation around the localized holes differs for anion and cation holes. The relaxation associated with Mn⁴⁺ is approximately isotropic, whereas ionic displacements around O^? holes show axial symmetry with the axis directed towards the apical oxygens. Using the Born-Haber cycle, we examine thermal and optical energies of the hole formation associated with the electron ionization from Mn³⁺, O^2?, and La³⁺ions in the LaMnO₃ lattice. For these calculations, we derive a phenomenological value for the second electron affinity of oxygen in the LaMnO₃ lattice by matching the optical energies of the La⁴⁺ and O^? hole formation with maxima of binding energies in the experimental photoemission spectra. The calculated thermal energies predict that the electronic hole is marginally more stable in the Mn⁴⁺ state in the LaMnO₃ host lattice, but the energy of a hole in the O^? state is only higher by a small amount, 0.75 eV, suggesting that both possibilities should be treated seriously. We examine the energies of a number of fundamental optical transitions, as well as those involving self-trapped holes of Mn⁴⁺ and O^? in the LaMnO₃ lattice. The reasonable agreement of our predicted energies, linewidths, and oscillator strengths with experimental data leads us to plausible assignments of the optical bands observed. We deduce that the optical band near 5 eV is associated with the O(2p)-Mn(3d) transition of a charge-transfer character, whereas the band near 2.3 eV is rather associated with the presence of Mn⁴⁺ and/or O^? self-trapped holes in the nonstoichiometric LaMnO₃ compound.     

Jahn-Teller effect for the 3A2-term

The first detection of the zero-phonon line (ZPL) structure in the absorption spectrum for an optical transition between the ³T₁ and ³A₂-terms (λ = 1.3–1.5 μm) is reported for CdS:Ni crystals. An analysis of the structure shows that its occurrence is due to the weak vibronic coupling of the ³A₂-state with trigonal pseudolocal vibrations of energy hω = 22 cm⁻¹, i.e. the dynamic Jahn-Teller (JT) effect is observed. The energy of the JT coupling is E_JT = 13 cm⁻¹. With E_JT < hω, a weak JT coupling takes place. Besides the ZPL, the absorption spectrum also involves other lines of vibronic nature which can be treated as dielectric local vibration modes. An axial pressure (P) is shown to lead to a change in the magnitude of E_JT: for P ∥ C(C being the optical axis of the crystal), E_JT increases, and for P ⊥ C, it decreases.     

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.     

Jahn-Teller transition and electron-phonon interaction in Cr-doped manganites Sr0.9Ce0.1Mn1−yCryO3

Cr-doped manganites Sr_0.9Ce_0.1Mn_1−yCr_yO₃ (y=0, 0.05, and 0.10) have been systematically investigated by X-ray, magnetic, transport, and elastic properties measurements. For parent compound Sr_0.9Ce_0.1MnO₃, it undergoes a metal-insulator (M-I) transition at 318 K, which is suggested to originate from a first-order structural transition accompanied by Jahn-Teller (JT) transition. With increasing Cr doping content, the JT transition temperature decreases. The Cr doping suppresses the antiferromagnetic (AFM) state and makes the system spin-glass (SG) behavior at low temperatures. In the vicinity of JT transition temperatures, the softening of Young's modulus originating from the coupling of the orbital (quadrupolar) moment of the e_g orbital of Mn³⁺ ion to the elastic strain has been observed. The anomalous Young's modulus properties imply the electron-phonon coupling due to the JT effect may play an important role in the system.     

Preparation and magnetic properties of LaMnO3 + δ (0 ≤ δ ≤ 0.154)

The structural, electrical, and magnetic properties of ceramic perovskite manganites LaMnO_{3 + δ} (δ = 0–0.154) are investigated. It is found that, in a weak magnetic field (B = 2 G), the LaMnO_{3 + δ} manganite with δ = 0.065 at temperatures below the Curie temperature T _C of the paramagnet-ferromagnet phase transition has a mixed (spin glass + ferromagnet) phase. In LaMnO_{3 + δ} manganites with the parameter δ = 0.100–0.154, this phase transforms into a frustrated ferromagnetic phase. A similar transformation was observed previously in La_1?x Ca_xMnO₃ compounds at calcium contents in the range 0 ≤ x ≤ 0.3. This similarity is explained by the fact that, in both materials, the Mn⁴⁺ concentration and, accordingly, the hole concentration c change equally in the concentration range from ～0.13 to 0.34 with an increase in x or δ. However, the magnetic irreversibility, the concentration dependences of the Curie temperature T _C(c) and the magnetic susceptibility X(c), and the critical behavior of the temperature dependence of the susceptibility X(T) in the vicinity of the Curie temperature T _C differ substantially for these two materials. The observed differences are associated with the distortion of the cubic perovskite structure, the decrease in the degree of lattice disorder, and a more uniform distribution of holes in the LaMnO_{3 + δ} manganites as compared to the La_{1 ? x} Ca_xMnO₃ compounds.     

The plasticity of the Cu(H2O) 6 2+ Jahn-Teller complex affected by lattice strains and cooperative interactions

The EPR spectra evolution of Cs₂Zn_1?x Cu_x(ZrF₆)₂ · 6H₂O (x=0.01, 0.6, 0.8, and 1.0) in the temperature range 4.2–330 K and the x-ray structure analysis of the compound with x=1.0 in the range 150–327 K show that the Jahn-Teller (JT) complex Cu(H₂O)₆ coordination sphere undergoes a plastic deformation. The observed effect is due to the combined influence of small lattice strains existing in the paraphase and a new one appearing as a result of a ferroelastic phase transition and increasing with decreasing temperature below T _c . It is proved that both cooperative interactions between JT complexes and ferroelastic strain stabilize a certain JT configuration. The problem of instability of a JT configuration compressed at T ～ 265 K is discussed.     

Resonant Raman scattering of polymeric sulfur nitride modified by iodine

Resonance Raman spectra of (SNI_y)_x crystals have been measured at 150 K. The energies of the principal Raman lines of the chromophore (109 and 154 cm^?1) and their intensity behaviour with exciting laser frequency are consistent with the formation of a charge-transfer complex in which iodine enters the interfiber regions of the (SN)_x lattice as I₅^- or I₃^- linked to distorted I₂ units. This structural model is supported by comparison of these Raman data with the excitation profiles of the chromophoric group in starch-iodine and α-cyclodextrine-iodine complexes. Possible mechanisms for the conductivity increase on the basis of the proposed charge transfer model are also discussed.     

Variable-temperature Raman scattering and X-ray diffraction studies of Bi3.25Nd0.75Ti3O12 ceramics

Neodymium-substituted bismuth titanate (Bi_3.25Nd_0.75Ti₃O₁₂, BNT_0.75) ceramics was prepared by chemical co-precipitation along with calcinations. The lattice instability has been investigated by variable-temperature Raman scattering and X-ray diffraction. The results showed that there was an orthorhombic to pseudo-tetragonal phase transition at about 695 K, in terms of the evolution of temperature dependence of Raman scattering frequencies. Some changes at about 695 K in the XRD lines, the lattice parameters (a, b, and c) as well as the orthorhombic distortion b/a have been detected in the high temperature X-ray diffraction, which confirmed the conclusion that the BNT_0.75 ceramics undergoes a ferroelectric to paraelectric phase transition at about 695 K.     

Helical magnetic structures in cubic perovskites

One-dimensional helical structures with a finite Hund interaction have been considered in detail. The analytical expressions for the electron spectrum of charge carriers in simplest one-dimensional and three-dimensional helical structures in a simple cubic lattice, which simulates the manganese sublattice in the crystal structure of perovskite, have been derived in the tight-binding approximation. It has been shown that this approach can explain qualitatively the formation of the antiferromagnetic A structure in LaMnO₃.     

Spin and orbital excitations in perovskite Mn oxides

An effective Hamiltonian of perovskite type LaMnO₃ is derived by taking into account the degeneracy ofe _g orbitals, Hund coupling and strong Coulomb interactions betweend-electrons in Mn ions. Spin and orbital excitations are calculated by using the effective Hamiltonian.     

Nanocomposites comprised of doped cerium dioxide and lanthanum manganite for syngas production

Nanocomposites comprised of fluorite-like (Gd- or Pr-doped ceria) and perovskite-like (LaMnO_3+δ) phases were prepared using a polymerized precursor (Pechini) route. Genesis of the structure of composites with annealing temperature has been studied by X-ray diffraction, Transmission Electron Microscopy and EXAFS. Up to 1300 °C, particle sizes of both fluorite and perovskite phases remain in the nano-range. Interaction between components is reflected in the increase of doped ceria lattice parameter and disordering of Mn coordination sphere. Despite this interaction, nanocomposites possess a high conductivity along with a high lattice oxygen mobility and reactivity. The addition of CoO improves sintering of nanocomposites.     

Raman scattering in brominated (SN)x crystals

Detailed Raman scattering data on brominated (SN)_x crystals ranging in composition from (SNBr_0.27)_x to (SNBr_0.55)_x, and preliminary Raman data on [SN(ICI)_0.125]_x are discussed. The investigation involved a study under various conditions of temperature, pressure and levels of bromination, of the two primary Raman lines at 154 and 230 cm^-1 in brominated (SN)_x, which are polarized along the polymer axis direction. The analysis of the data is consistent with a model in which bromine enters the interfibrillar regions as Br^-₃ and the (SN)_x lattice as Br₂. Infrared data is also presented showing an appreciable decrease in intensity of the SN modes at 995 and 670 cm^-1 on bromination.     

Raman spectroscopic study of the lattice dynamics in the Rb2KMoO3F3 oxyfluoride

The lattice dynamics of the Rb₂KMoO₃F₃ oxyfluoride has been studied by Raman spectroscopy in the temperature range 7–400 K. A phase transition has been revealed at T ≈ 185 K with decreasing temperature. Anomalies of the frequencies and Raman line half-widths have been analyzed. No condensation of soft lattice modes has been found. The character of changes in the Raman spectra of the Rb₂KMoO₃F₃ oxyfluoride shows that the phase transition is related to variations in the [MoO₃F₃]^3? molecular octahedron.     

Effect of cation doping on low-temperature specific heat of LaMnO3 manganite

We have investigated the thermodynamic properties of perovskite manganite LaMnO₃, the parent compound of colossal magnetoresistive manganites, with the Ca²⁺ doping at the A-site. As strong electron-phonon interactions are present in these compounds, the lattice part of the specific heat deserves proper attention. We have described the temperature dependence of the lattice contribution to the specific heat at constant volume (C_v(lattice)) of La_1−xCa_xMnO₃ (x=0.125, 0.175, 0.25, 0.35, 0.50, 0.67, 0.75) as a function of temperature (1 K–20 K) by means of a rigid ion model (RIM).The trends of specific heat variations with temperature are almost similar at all the composition. The Debye temperatures obtained from the lattice contributions are found to be in somewhat closer agreement with the experimental data. The specific heat values revealed by using RIM are in closer agreement with the available experimental data, particularly at low temperatures for some concentrations (x) of La_1−xCa_xMnO₃. The theoretical results at higher temperatures can be improved by including the effects of the charge ordering, van der Waals attraction and anharmonicity in the framework of RIM.     

Effect of nanosizing on lattice and magnon modes of hematite

Broadening of Raman lines and a decrease of frequencies relative to the bulk material are observed for the lattice modes of nanoparticles of the hematite phase of Fe₂O₃. The magnon mode frequency is observed to shift up with reduced particle size in contrast to the lattice modes. The effects are suggested to be a result of phonon confinement and represent the first observation of phonon confinement effects on magnon modes. The Fe₂O₃ nanoparticles are produced by laser decomposition of Fe₃O₄ nanoparticles. X-ray diffraction and Raman frequency shifts indicate the Fe₂O₃ nanoparticles are smaller than the parent Fe₃O₄ nanoparticles.     

The cubic-to-monoclinic phase transition in (NH4)3ScF6 cryolite: A Raman scattering study

This paper reports on a Raman study of the cubic-to-monoclinic phase transition in (NH₄)₃ScF₆ cryolite. We observed sharp anomalies in the frequencies and half-widths of the Raman lines corresponding to internal vibrations of the ScF ₆ ³⁺ ions and to lattice vibrations; no soft lattice mode condensation was revealed. It is concluded that the phase transition studied is related primarily to the orientational ordering of these ions.