Internal friction evidence of uncorrelated magnetic clusters in electron-doped manganite Sr0.8Ce0.2MnO3

Electron-doped manganite Sr_0.8Ce_0.2MnO₃ has been systematically investigated by X-ray diffraction, electronic transport, magnetic, internal friction, and Young's modulus experiments. The X-ray diffraction result indicates that the compound remains tetragonal (I4/mcm) structure at room temperature. Due to the strong Jahn–Teller (JT) distortion, the ground state is antiferromagnetic (AFM) insulator. Below 20 K, a spin-glass (SG) state dominates at low temperatures. In the paramagnetic (PM) region, an internal friction peak at around 250 K, which is characteristic of relaxation, has been observed. Under applied magnetic field, the internal friction peak moves to higher temperature, which is suggested to originate from the formation of ferromagnetic (FM) clusters in PM region. In addition, the softening of Young's modulus in the vicinity of AFM transition temperature is interpreted in terms of the strong electron–phonon interaction.     

Elastic-effects study of charge-ordering transition in La0.25Ca0.75MnO3 perovskite

The temperature dependence of the elastic properties of polycrystalline manganites La_0.25Ca_0.75MnO₃ has been studied by means of ultrasonic measurements and low-frequency internal friction apparatus. It was found that both the longitudinal modulus and the low frequency shear modulus starts to soften obviously with decreasing temperature from higher temperature to the charge-ordering transition temperature T_CO, and stiffens dramatically just below T_CO. The abnormal temperature dependence of the elastic modulus around T_CO is fitted with the mean-field theory, which describes the coupling of Jahn–Teller ions to distortions of lattice of the cooperative Jahn–Teller system. The good fit of the theory to the data indicates that the Jahn–Teller effect is the dominant mechanism responsible for the charge–ordering state of the system.     

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.     

Thermal conductivity and infrared spectra study of polycrystalline La0.67Ca0.33MnO3

The thermal conductivity and infrared transmission spectra of La_0.67Ca_0.33MnO₃ are investigated systematically. The thermal conductivity increases abruptly as the temperature is decreased through the Curie temperature. The effective charge carriers number and the frequency of transverse optic phonon corresponding to the stretching mode also increase dramatically along with decreasing temperature near Curie temperature. Combining our observation with previous reported results, we ascribe the abrupt change of thermal conductivity to the itinerating of the charge carriers due to the remarkable reduction of Jahn–Teller distortion below the Curie temperature.     

Electron spin resonance study of a CuIr2S4 single crystal

A spinel sulphide CuIr₂S₄ single crystal, which exhibits an orbitally induced Peierls phase transition at ～230?K, is investigated by electron spin resonance (ESR) spectroscopy. The phase transition is clearly manifested on the ESR spectra. It is suggested that the ESR signals are produced by a few non-dimerized Ir⁴⁺ ions. Moreover, an extra ESR spectrum appears at low temperature in addition to the paramagnetic ESR signals of Ir⁴⁺ ions, which is suggested to be caused by the Jahn–Teller effect of the non-dimerized Ir⁴⁺ ions. From the ESR results, it is found that the Jahn–Teller splitting energy ΔE _JT is much smaller than the spin-dimerization gap.     

Structural,electrical, magnetic,elastic, and internal friction studies of Nd1−xCaxMnO3 (x=0.2, 0.33, 0.4, and 0.5) manganites

A series of Nd_1?xCa_xMnO₃ (x=0.2, 0.33, 0.4, and 0.5) manganites was prepared by sol–gel route by sintering at 1300 °C, mainly to understand the correlation between electron, spin, and phonon couplings. The internal friction and longitudinal modulus along with electrical and magnetic properties have been measured. All the samples are found to exhibit anomalies at T_C, T_N, and T_CO transition temperatures. The anomalies in longitudinal modulus and the internal friction peak at T_CO are attributed to Jahn–Teller effect. A strong correlation between the temperature dependent elastic, anelastic, resistivity, and ac susceptibility properties has been observed and an effort has been made to explain the observed anomalous behavior by a qualitative model.     

Simultaneous structural,magnetic, and electronic transition and electronic structure in La0.85Na0.15MnO3

The lattice parameters, magnetization and electronic resistivity of La_0.85Na_0.15MnO₃ as a function of temperature were investigated. A simultaneous structural, magnetic, and electronic transition was observed. We argued that this is the result of strong electron–lattice coupling and may be a trace of Jahn–Teller distortion. X-ray photoelectron valence-band spectra measurement at room temperature is also carried out and its results suggest the mobile charge carries had localized below T_C.     

Jahn—Teller coupling in the [Xtilde] 2E ground states of the CF3O and CF3S radicals

The Jahn—Teller and spin—orbit coupling in the ground states of the CF₃O and CF₃S radicals have been investigated experimentally by dispersed fluorescence spectroscopy. These spectra are analysed using a theoretical model that simultaneously includes spin—orbit coupling and multimode Jahn—Teller coupling, both linear and quadratic. We find that in each of these radicals a moderate linear Jahn—Teller effect exists in ν₆, with a much smaller coupling in ν₅. These results are compared and contrasted with those for the related radicals CH₃O and CH₃S. The experimental data and theoretical analyses of these four radicals represent the most thorough investigations to date of the combined effects of spin—orbit and Jahn—Teller coupling.     

Tc map and superconductivity of simple metals at high pressure

We calculate T_c map in region of weak electron–phonon coupling based on simple phonon spectrum. By using linear-response method and density functional theory, we calculate phonon spectra and Eliashberg functions of simple metals under pressure. Based on the evolutions of superconducting parameters of simple metals on the T_c map with increasing pressure, we find that there are two different responses to pressure for simple metals: (1) enhancing electron–phonon interaction λ such as for La and Li, (2) increasing phonon frequency such as for Pb, Pt. The λ threshold effect is found, which origins from the competition between electron–phonon interaction and electron–electron Coulomb interaction and is the reason why T_c of most superconductors of simple metals are higher than 0.1 K.     

The specific heat of potassium holmium double tungstate

The results of measurements of thermal properties (specific heat) of potassium holmium double tungstate KHo(WO₄)₂ as a function of temperature (from 0.5 to 300?K) and magnetic field (up to 2?T) are presented. The total specific heat without the phonon and Schottky contributions is found to have the anomaly with maximum at T _SPT?～?5?K. This anomaly is likely related with the structural phase transition (SPT) caused by the cooperative Jahn–Teller effect. The increase of specific heat at very low temperatures and its shift towards high temperatures with increasing magnetic field are observed. The origin of this behaviour can be connected with possible magnetic phase transition induced by magnetic field.     

Why are cuprates the only high-temperature superconductors?

The hierarchical mean-field theory of elastic networks, originally developed by Maxwell to discuss the stability of scaffolds, and recently applied to atomic networks by Phillips and Thorpe, explains the phase diagrams and remarkable superconductive properties of cuprates as the result of giant electron–phonon interactions in a marginally unstable mechanical network. The overall cuprate networks are fragile (floppy), as shown quantitatively (with an accuracy of about 1%), and without adjustable parameters, by comparison with stabilities of generically similar network glasses. Jahn–Teller distortions that would render the material insulating are suppressed by percolative backbones composed of isostatic CuO₂ planes. The model has many applications, including isotopic and dopant dependencies measured near photoemission ‘kinks’.     

Novel aspects of charge and lattice dynamics in the hole-doped manganite La0.67Sr0.33MnO3

Previous infrared studies on the hole-doped manganite La_0.67Sr_0.33MnO₃ (LSMO) have analysed its charge dynamics in terms of one type of charge carrier despite evidence of both electron and hole Fermi surfaces. Here, we investigate the charge dynamics of an LSMO film with infrared and optical spectroscopy in order to provide a complete picture of metallic conduction. In the ferromagnetic metallic phase, the low-frequency optical conductivity is best explained by a two-carrier model comprising electrons and holes. The number densities, effective masses and relaxation response of the delocalized electrons and holes are quantified. We discover that only one-third of the doped charges are coherent and contribute to the dc transport. Metallic LSMO cannot be classified as a bad metal at low temperatures because the mean free path of the coherent, mobile charge carriers exceeds the Ioffe–Regel–Mott limit. The incoherent spectral response of the doped charges manifests itself as a broad mid-infrared feature. We also report the first observation of splitting of an infrared-active phonon due to local Jahn–Teller distortion in the vicinity of the thermally driven transition to the nonmetallic, paramagnetic phase in LSMO. This demonstrates that infrared spectroscopy is capable of detecting the presence of local lattice distortions in correlated electron systems.     

Micro‐Raman study of orbiton–phonon coupling in YbVO3

First‐order and multiphonon Raman active excitations are studied in YbVO₃ as a function of temperature in the orthorhombic and monoclinic phases. Below T ≃ 170 K, a G‐type orbital ordering with a concomitant monoclinic transition occurs. They enhance the phonon polarizabilities, allowing the resolution of room‐temperature bands, and activate new excitations around 700 cm⁻¹. Below T ∼ 65 K, the 700 cm⁻¹ excitations disappear, indicating a C‐type orbital ordering and a return to the orthorhombic structure. The observed phonon combinations around 1400 cm⁻¹ with a dominant Jahn‐Teller vibration at ∼690 cm⁻¹ reflect a possible orbiton‐phonon coupling. Copyright © 2011 John Wiley & Sons, Ltd.     

Magnetic properties of Nd0.5Pb0.5—xSrxMnO3 materials

The structure and magnetic properties of Nd_{0.5}Pb_{0.5-x}Sr_xMnO_3 (0≤x≤0.4) manganites were systematically investigated. Significant changes in Curie temperature and metal-insulator (MI) transition temperature of the samples were observed. All samples exhibited a transition from paramagnetic semiconducting to ferromagnetic metallic state. Curie temperature T_C and the MI transition temperature T_p increased with increasing Sr content. We attributed these behaviours to the enhancing of both the double exchange mechanism and the Jahn－Teller electron－phonon coupling.     

Exchange interaction and Jahn—Teller correlations in novel tetranuclear supramolecular Cu(II) grid complexes: an ESR study

Novel tetranuclear Cu(II) complexes in which four Cu(II) ions are arranged in a square planar fashion by four bis(bipyridyl)pyrimidine ligands were investigated by X and Q band ESR in the temperature range 4.2-300 K. The ESR spectra of this grid-like structure were well simulated as rising from triplet species. Analysis of their intensities allowed the spectra to be assigned to the first excited triplet state, and revealed intramolecular antiferromagnetic coupling of the Cu(II) spins. The isotropic exchange interaction J was determined as ?47 K and reducing to about ?5 K on functionalizing the bridging pyrimidine ring at the 2-position by methyl or phenyl. For comparison an ESR investigation was also carried out on the mononuclear analogue Cu(II)—(terpyridine)₂ complexes with substituted terpyridine ligands at the 5′ and 5″ position. Depending on the substitutent, the spectra exhibit a static or dynamic Jahn—Teller effect at room temperature. The temperature dependence of their g-values is examined by a modified Silver—Getz model which includes cooperative Jahn—Teller interactions. There is evidence that both an anisotropic spin exchange contribution to D = 0.0159 cm^?1 and a coupled (static) Jahn—Teller effect are responsible for efficient coupling between the four Cu(II) ions in the grid complexes with non-substituted pyrimidine bridges.     

Theory studies of the local lattice distortions and the EPR parameters for Cu2+, Mn2+ and Fe3+ centres in ZnWO4

The local lattice distortions and the electron paramagnetic resonance (EPR) parameters (g factors, hyperfine structure constants and zero-field splittings) for Cu²⁺, Mn²⁺ and Fe³⁺ in ZnWO₄ are theoretically studied based on the perturbation calculations for rhombically elongated octahedral 3d⁹ and 3d⁵ complexes. The impurity centres on Zn²⁺ sites undergo the local elongations of 0.01, 0.002 and 0.013 Å along the C₂ axis and the planar bond angle variations of 8.1°, 8.0° and 8.6° for Cu²⁺, Mn²⁺ and Fe³⁺, respectively, due to the Jahn–Teller effect and size and charge mismatch. In contrast to the host Zn²⁺ site with obvious axial elongation (～0.31 Å) and perpendicular (angular) rhombic distortion, all the impurity centres demonstrate more regular octahedral due to the above local lattice distortions. The copper centre exhibits significant Jahn–Teller reductions for the spin-orbit coupling and orbital angular momentum interactions, characterised by the Jahn–Teller reduction factor J (≈0.29 ? 1). The calculated EPR parameters agree well with the experimental results. The local structures of the impurity centres are analysed in view of the corresponding lattice distortions.     

Enhanced Fröhlich interaction of semiconductor cuprous oxide films determined by temperature‐dependent Raman scattering and spectral transmittance

Anomalous low temperature behaviors in cuprous oxide (Cu₂O) film grown on quartz substrate have been investigated by temperature‐dependent Raman and transmittance spectra. The longitudinal optical components of two Γ₁₅‐ phonon modes become sharper and more intense at a low temperature. It can be found that the highest‐order electronic transition located at 6.4 eV exhibits a minimum transmittance near 200 K. Correspondingly, the variations from phonon intensity ratios reveal obvious anomalies with the decreasing temperature, indicating the existence of strong electron–phonon coupling mediated by Fröhlich interaction in the Cu₂O films below the temperature of 200 K. Copyright © 2012 John Wiley & Sons, Ltd.     

Contribution from structural Jahn–Teller ions to the elastic and ferroelectric properties of lithium niobate and lithium tantalate

Elastic and ferroelectric characteristics of single crystals of lithium niobate and tantalate are investigated in a wide range of temperatures by complex acoustooptic means. The contribution from Jahn–Teller NbO₆ and TaO₆ systems to the characteristics of elastic moduli, ultrasonic attenuation, and nonlinear optical coefficients is analyzed using a new phenomenological model. It is hypothesized that the displacement of Nb⁵⁺ and Ta⁵⁺ ions, which exhibit the second-order Jahn–Teller effect along trigonal axis C, and the subsequent ordering of octahedral, result in unusual elastic and ferroelectric properties.     

Theoretical investigations of the spin Hamiltonian parameters for the CoCl(PPh3)3 molecules

The perturbation formulas of the spin Hamiltonian parameters (zero-field splitting and g factor g_// and g_⊥) are established for a 3d⁸ ion in trigonally distorted tetrahedra for the first time. In the theoretical treatments, the contributions from the Jahn–Teller effect, the ligand orbital and spin–orbit coupling interactions and configuration interactions are taken into account from the cluster approach in a uniform way. The above formulas are applied to the studies of the spin Hamiltonian parameters for the three CoCl(PPh₃)₃ molecules, and the experimental electron paramagnetic resonance spectra of all the molecules are satisfactorily explained. The significant compressions of the ligand tetrahedra with mixed chlorine and PPh₃ groups around Co⁺ are analysed for three distinct CoCl(PPh₃)₃ compounds, characterised by the Cl–Co–P bond angles θ larger than the tetrahedral angle of 109.47°. The local trigonal distortions are discussed in view of the Jahn–Teller effect.