Determinative Role of the Jahn-Teller Disorder in the Raman Scattering of Mixed-Valence Manganites

The mixed-valence perovskitelike manganites are characterized by unique interrelation of Jahn-Teller distortions, electric and magnetic properties. The Jahn-Teller distortion follows the Mn(3+)->Mn(4+) charge transfer with some delay. Its development depends on the lifetime of Mn in (3+) state, governed by the Mn(4+)/Mn(3+) ratio and magnetic correlation. The non-coherence of Jahn-Teller distortions in orthorhombic mixed-valence manganites and rhombohedral RMnO3 (R = rare earth) results in oxygen disorder. We demonstrate that the Raman spectra in this case are dominated by disorder-induced bands reflecting the oxygen partial phonon density of states (PDOS). The PDOS origin of the main Raman bands in insulating phases of such compounds is evidenced by the similar lineshape of experimental spectra and calculated smeared PDOS and disappearance of the PDOS bands in ordered ferromagnetic metallic phase.Comment: 4 pages, 3 figure

Short-Range B-site Ordering in Inverse Spinel Ferrite NiFe2O4

The Raman spectra of single crystals of NiFe2O4 were studied in various scattering configurations in close comparison with the corresponding spectra of Ni0.7Zn0.3Fe2O4 and Fe3O4. The number of experimentally observed Raman modes exceeds significantly that expected for a normal spinel structure and the polarization properties of most of the Raman lines provide evidence for a microscopic symmetry lower than that given by the Fd-3m space group. We argue that the experimental results can be explained by considering the short range 1:1 ordering of Ni2+ and Fe3+ at the B-sites of inverse spinel structure, most probably of tetragonal P4_122/P4_322 symmetry.Comment: 10 pages, 5 figures, 6 table

Gold catalysts supported on ceria doped by rare earth metals for water gas shift reaction: Influence of the preparation method

Cataloged from PDF version of article.Gold catalysts based on ceria, doped by various RE metals (La, Sm, Gd, Yb, Y) were studied. The influence of the preparation methods on structure, properties and catalytic activity in the WGS reaction was investigated. The catalysts' supports were prepared using two different methods: co-precipitation (CP) and mechanochemical activation (MA). The catalysts were tested in a wide temperature interval without and after reactivation. All samples were characterized using a combination of X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM), Raman spectroscopy (RS) and X-ray photoelectron spectroscopy (XPS) and TPR. It was found that the catalytic activity of MA catalysts is higher than CP ones. The gold catalysts based on ceria doped by Yb and Sm exhibited the highest activity. After reactivation in air the MA samples almost kept the WGS activity same, while the CP catalysts increased it. The catalysts of a single- and double-phase structure are formed as a result of CP and MA preparation, respectively. There are no big differences in the gold particles size (2-3 nm) depending on dopants and on the preparation techniques. The RS spectra analysis indicates that most probably the oxygen vacancies are adjacent to Me(3+) dopant and the ceria structure seems to be better ordered than in the case of alumina as a dopant. There is no distinct correlation between reducibility and WGS activity. The XPS analysis disclose positively charged gold particles in addition to metallic gold within a surface region of fresh samples and only metallic gold on the samples after catalytic processing. There is no simple correlation between the concentration of Ce(3+) in the samples and their WGS activity. (C) 2009 Elsevier B.V. All rights reserved

Phonons and Magnetic Excitations in Mott-Insulator LaTiO3_3

The polarized Raman spectra of stoichiometric LaTiO$_3$ (T$_N = 150$ K) were measured between 6 and 300 K. In contrast to earlier report on half-metallic LaTiO$_{3.02}$, neither strong background scattering, nor Fano shape of the Raman lines was observed. The high frequency phonon line at 655 cm$^{-1}$ exhibits anomalous softening below T$_N$: a signature for structural rearrangement. The assignment of the Raman lines was done by comparison to the calculations of lattice dynamics and the nature of structural changes upon magnetic ordering are discussed. The broad Raman band, which appears in the antiferromagnetic phase, is assigned to two-magnon scattering. The estimated superexchange constant $J = 15.4\pm0.5$ meV is in excellent agreement with the result of neutron scattering studies.Comment: 4 pages, 5 figure

Quantum Spin Systems: From Spin Gaps to Pseudo Gaps

Many low dimensional spin systems with a dimerized or ladder-like antiferromagnetic exchange coupling have a gapped excitation spectrum with magnetic bound states within the spin gap. For spin ladders with an even number of legs the existence of spin gaps and within the t-J model a tendency toward superconductivity with d-wave symmetry is predicted. In the following we will characterize the spin excitation spectra of different low dimensional spin systems taking into account strong spin phonon interaction ($\rm CuGeO_3$), charge ordering ($\rm NaV_2O_5$) and doping on chains and ladders (\ladder). The spectroscopic characterization of the model systems mentioned above has been performed using magnetic inelastic light scattering originating from a spin conserving exchange scattering mechanism. This is also bound to yield more insight into the interrelation between these spin gap excitations and the origin of the pseudo gap in high temperature superconductors.Comment: 10 pages, 5 figure

Silver Flowerlike Structures for Surface-Enhanced Raman Spectroscopy

Micro-and nanoflowers are a class of materials composed of particles with high surface-to-volume ratio. They have been extensively studied in the last decade due to simple preparation protocols and promising applications in biosensing, as drug delivery agents, for water purification, and so on. Flowerlike objects, due to their highly irregular surface, may act also as plasmonic materials, providing resonant coupling between optical waves and surface plasmon excitations. This fact allows us to infer the possibility to use micro-and nanoflowers as effective surface-enhanced Raman scattering (SERS) substrate materials. Here, we report on the design and Raman enhancement properties of silver flowerlike structures, deposited on aluminum surface. A simple and cost-effective fabrication method is described, which leads to SERS substrates of high developed surface area. The morphology of the silver flowers on a nanoscale is characterized by self-organized quasiperiodic stacks of nanosheets, which act as plasmonic cavity resonators. The substrates were tested against rhodamine-6G (R6G) water solutions of concentration varying between 10−3 M and 10−7 M. Optimal SERS enhancement factors of up to 105 were established at R6G concentrations in the 10−6–10−7 M range. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.This research was funded by the Bulgarian-Russian bilateral project through the contracts KP-06-15/27.09.2019 Russia with the Bulgarian National Fund of Scientific Research (G.G.T, N.D.T., S.C.R., and V.G.I.) and RFBR project No. 19-52-18008 Bulg (A.V.L.)

Non-perturbative effective field theory for two-leg antiferromagnetic spin ladders

We study the long wavelength limit of a spin 1/2 Heisenberg antiferromagnetic two-leg ladder, treating the interchain coupling in a non-perturbative way. We perform a mean field analysis and then include exactly the fluctuations. This allows for a discussion of the phase diagram of the system and provides an effective field theory for the low energy excitations. The coset fermionic Lagrangian obtained corresponds to a perturbed SU(4)_1/U(1) Conformal Field Theory (CFT). This effective theory is naturally embedded in a SU(2)_2 x Z_2 CFT, where perturbations are easily identified in terms of conformal operators in the two sectors. Crossed and zig-zag ladders are also discussed using the same approach.Comment: 14 pages LaTeX, 5 PostScript figures included using epsfig.sty; minor corrections and a few references adde

Optical studies of gap, hopping energies and the Anderson-Hubbard parameter in the zigzag-chain compound SrCuO2

We have investigated the electronic structure of the zigzag ladder (chain) compound SrCuO2 combining polarized optical absorption, reflection, photoreflectance and pseudo-dielectric function measurements with the model calculations. These measurements yield an energy gap of 1.42 eV (1.77 eV) at 300 K along (perpendicular) to the Cu-O chains. We have found that the lowest energy gap, the correlation gap, is temperature independent. The electronic structure of this oxide is calculated using both the local-spin-density-approximation with gradient correction method, and the tight-binding theory for the correlated electrons. The calculated density of electronic states for non-correlated and correlated electrons shows quasi-one-dimensional character. The correlation gap values of 1.42 eV (indirect transition) and 1.88 eV (direct transition) have been calculated with the electron hopping parameters t = 0.30 eV (along a chain), t_yz = 0.12 eV (between chains) and the Anderson-Hubbard repulsion on copper sites U= 2.0 eV. We concluded that SrCuO_2 belongs to the correlated-gap insulators.Comment: 24 pages, 8 figures, to be published in Phys.Rev.

Gold catalysts supported on ceria doped by rare earth metals for water gas shift reaction: Influence of the preparation method

Gold catalysts based on ceria, doped by various RE metals (La, Sm, Gd, Yb, Y) were studied. The influence of the preparation methods on structure, properties and catalytic activity in the WGS reaction was investigated. The catalysts' supports were prepared using two different methods: co-precipitation (CP) and mechanochemical activation (MA). The catalysts were tested in a wide temperature interval without and after reactivation. All samples were characterized using a combination of X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM), Raman spectroscopy (RS) and X-ray photoelectron spectroscopy (XPS) and TPR. It was found that the catalytic activity of MA catalysts is higher than CP ones. The gold catalysts based on ceria doped by Yb and Sm exhibited the highest activity. After reactivation in air the MA samples almost kept the WGS activity same, while the CP catalysts increased it. The catalysts of a single- and double-phase structure are formed as a result of CP and MA preparation, respectively. There are no big differences in the gold particles size (2-3 nm) depending on dopants and on the preparation techniques. The RS spectra analysis indicates that most probably the oxygen vacancies are adjacent to Me3+ dopant and the ceria structure seems to be better ordered than in the case of alumina as a dopant. There is no distinct correlation between reducibility and WGS activity. The XPS analysis disclose positively charged gold particles in addition to metallic gold within a surface region of fresh samples and only metallic gold on the samples after catalytic processing. There is no simple correlation between the concentration of Ce3+ in the samples and their WGS activity. © 2009 Elsevier B.V. All rights reserved