Dimerization and low-dimensional magnetism in nanocrystalline TiO2 semiconductors doped by Fe and Co

The report is devoted to an analysis of the structural and magnetic state of the nanocrystalline diluted magnetic semiconductors based on TiO2 doped with Fe and Co atoms. Structural and magnetic characterization of samples was carried out using X-ray diffraction (XRD) analysis, transmission electron microscopy (TEM), X-ray absorption spectroscopy (XAS), electron paramagnetic resonance (EPR) spectroscopy, SQUID magnetometry, and the density functional theory (DFT) calculations. Analysis of the experimental data suggests the presence of non-interacting paramagnetic Fe3+ and Co2+ ions in the high-spin state and negative exchange interactions between them. The important conclusions is that the distribution of dopants in the TiO2 matrix, even at low concentrations of 3d-metal dopant (less than one percent), is not random, but the 3d ions localization and dimerization is observed both on the surface and in the nanoparticles core. Thus, in the paper the quantum mechanical model for describing the magnetic properties of TiO2:(Fe, Co) was suggested. The model operates only with two parameters: paramagnetic contribution of non-interacting 3d-ions and dimers having different exchange interactions between 3d magnetic carriers. © Published under licence by IOP Publishing Ltd

Unconventional magnetism of non-uniform distribution of Co in TiO2 nanoparticles

High-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD) analysis, electron paramagnetic resonance (EPR), X-ray absorption spectroscopy (XAS), magnetic methods, and density-functional theory (DFT) calculations were applied for the investigations of Co-doped anatase TiO2 nanoparticles (∼20 nm). It was found that high-spin Co2+ ions prefer to occupy the interstitial positions in the TiO2 lattice which are the most energetically favourable in compare to the substitutional those. A quantum mechanical model which operates mainly on two types of Co2+ – Co2+ dimers with different negative exchange interactions and the non-interacting paramagnetic Co2+ ions provides a satisfactorily description of magnetic properties for the TiO2:Co system. © 2020 Elsevier B.V.Russian Foundation for Basic Research. Ministry of Science and Higher Education of the Russian Federatio

Spin States of Cobalt Ions in the Bulk and on the Surface of LaCoO3 Probed by X-ray Absorption, Emission, and Photoelectron Spectra

We present X-ray photoelectron, Co L2,3 and O K X-ray absorption, as well as Co Kβ1,3 X-ray emission spectroscopy results of studies of the spin states of trivalent cobalt ions in single-crystal cobaltite LaCoO3. We show that at room temperature, in the bulk of a LaCoO3 single crystal, Co3+ ions are in the low-spin state, while high-spin Co2+, high-spin Co3+, low-spin Co3+ , and probably also intermediate-spin Co3+ ions are localated on the surface

Electronic Structure of Transition-Metal Dicyanamides Me[N(CN)2_2]2_2 (Me = Mn, Fe, Co, Ni, Cu)

The electronic structure of Me[N(CN)$_2$]$_2$ (Me=Mn, Fe, Co, Ni, Cu) molecular magnets has been investigated using x-ray emission spectroscopy (XES) and x-ray photoelectron spectroscopy (XPS) as well as theoretical density-functional-based methods. Both theory and experiments show that the top of the valence band is dominated by Me 3d bands, while a strong hybridization between C 2p and N 2p states determines the valence band electronic structure away from the top. The 2p contributions from non-equivalent nitrogen sites have been identified using resonant inelastic x-ray scattering spectroscopy with the excitation energy tuned near the N 1s threshold. The binding energy of the Me 3d bands and the hybridization between N 2p and Me 3d states both increase in going across the row from Me = Mn to Me = Cu. Localization of the Cu 3d states also leads to weak screening of Cu 2p and 3s states, which accounts for shifts in the core 2p and 3s spectra of the transition metal atoms. Calculations indicate that the ground-state magnetic ordering, which varies across the series is largely dependent on the occupation of the metal 3d shell and that structural differences in the superexchange pathways for different compounds play a secondary role.Comment: 20 pages, 11 figures, 2 table

ELECTRONIC STRUCTURE OF FeSi

The full set of high-energy spectroscopy measurements including X-ray photoelectron valence band spectra and soft X-ray emission valence band spectra of both components of FeSi (Fe K_beta_5, Fe L_alpha, Si K_beta_1,3 and Si L_2,3) are performed and compared with the results of ab-initio band structure calculations using the linearized muffin-tin orbital method and linearized augmented plane wave method.Comment: 11 pages + 3 PostScript figures, RevTex3.0, to be published in J.Phys.:Cond.Matte

Electrical resistivity, magnetism and electronic structure of the intermetallic 3d/4f Laves phase compounds ErNi2Mnx

The non-stoichiometric intermetallic compounds RENi2Mnx (RE = rare earth) with the cubic MgCu2-type structure display a large variety of magnetic properties which is due to a complex interplay between the degrees of freedom of the 3d and 4f electrons and their interactions. We performed a comprehensive study of the electrical resistivity, magnetic properties and the electronic structure of ErNi2Mnx (x =0, 0.25, 0.5, 0.75, 1, 1.25) compounds by employing a suitable set of complementary experimental approaches. We find an increase in electrical resistance compared to ErNi2 upon Mn doping, the residual resistivity ratio decreases with increasing manganese content. The Curie temperature exhibits a sharp increase to around 50 K for Mn concentrations x 0.5, whereas the saturation magnetization decreases with growing Mn content x 0.5. Valence band X-ray photoelectron spectroscopy reveals an increasing intensity of Mn 3d states near Fermi energy in dependence of Mn concentration and Curie temperature. Resonant photoelectron spectroscopy of ErNi2Mn0.75 reveals that the photoemission decay channels dominate the valence band spectra across the Er N5 and Mn L3 X-ray absorption maxima, whereas the L3VV Auger dictates the resonant valence band spectra close to and at the Ni L3 X-ray absorption edge

On 3d extensions of AGT relation

An extension of the AGT relation from two to three dimensions begins from connecting the theory on domain wall between some two S-dual SYM models with the 3d Chern-Simons theory. The simplest kind of such a relation would presumably connect traces of the modular kernels in 2d conformal theory with knot invariants. Indeed, the both quantities are very similar, especially if represented as integrals of the products of quantum dilogarithm functions. However, there are also various differences, especially in the "conservation laws" for integration variables, which hold for the monodromy traces, but not for the knot invariants. We also discuss another possibility: interpretation of knot invariants as solutions to the Baxter equations for the relativistic Toda system. This implies another AGT like relation: between 3d Chern-Simons theory and the Nekrasov-Shatashvili limit of the 5d SYM.Comment: 23 page

Correlation Effects on Optical Conductivity of FeSi

Effects of electron correlation in FeSi are studied in terms of the two-band Hubbard model with the density of states obtained from the band calculation. Using the self-consistent second-order perturbation theory combined with the local approximation, the correlation effects are investigated on the density of states and the optical conductivity spectrum, which are found to reproduce the experiments done by Damascelli et al. semiquantitatively. It is also found that the peak at the gap edge shifts to lower energy region by correlation effects, as is seen in the experiments.Comment: 4 pages, 3 figure