X-ray absorption spectroscopy at the L-edge probes transitions of 2p-electrons into unoccupied d-states. Applied to transition metal atoms, this experimental technique can provide valuable information about the electronic structure of d-states. However, multiplet effects, spin-orbit coupling, a large number of possible transitions can cause a rather involved nature of 2p XAS spectra, which can often complicate extracting of information directly from them. Here, artificial neural networks trained on simulated spectra of a 2p XAS model Hamiltonian are presented that can directly determine information about atomic properties and the electronic configuration of d-states from L-edge X-ray absorption spectra. Moreover, the adaptable nature of artificial neural networks (ANNs) allows extending their capability to obtain information about the electronic ground state and core hole lifetimes from 2p XAS spectra as well as to incorporate external factors, such as temperature and experimental convolution that can affect details in spectral features. The effects of noise and background contributions in spectra on the accuracy of ANNs are discussed and the method is validated on experimental spectra of transition metal compounds, including metal-organic molecules and metal oxides.
As a possible alternative to organic-inorganic hybrid perovskite halide, inorganic Cs2SnI6 has drawn more and more research attention recently. In order to find more Cs2SnI6 derivatives as the potential solar cell absorber materials, I- ions in Cs2SnI6 are replaced by other halogen ions and forms the Cs2SnI6-nXn (X=F, Cl, Br; n=1~6) compounds, whose atomic structures, electronic structures and optical absorption are investigated by first principles calculation. When the alloying level n increases, the mean lattice constants, the weighted Sn-X and Cs-X bond lengths all decreases linearly; the b…
We analyze the linear absorption spectrum of regioregular poly(3-hexylthiophene) films spun from a variety of solvents to probe directly the film microstructure and how it depends on processing conditions. We estimate the exciton bandwidth and the percentage of the film composed of aggregates quantitatively using a weakly interacting H-aggregate model. This provides a description of the degree and quality of crystallites within the film and is in turn correlated with thin-film field-effect transistor characteristics.
A universal theoretical model is proposed that explains the observed shift of IR absorption and emission bands in the spectra of transition metal ions in solid solutions of semiconductor compounds. The model has been used for estimating the long-wavelength shift of luminescence bands in the spectra of semiconductor solid solutions with increasing concentration in application to crystals of the ternary systems ZnMgSe(Cr2+) and CdMnTe(Fe2+). Description of the phenomenon is generalized to the case of multicomponent solid solutions.
In this paper we develop a technique for determining interatomic potentials in materials in the quantum regime from single--shell Extended X-ray Absorption Spectroscopy (EXAFS) spectra. We introduce a pair distribution function, based on ordinary quantum time--independent perturbation theory. In the proposed scheme, the model potential parameters enter the distribution through a fourth--order Taylor expansion of the potential, and are directly refined in the fit of the model signal to the experimental spectrum. We discuss in general the validity of our theoretical framework, namely the quantum…
Designing high potential cathodes for Na-ion batteries, which are comparable in performance to Li-ion cathodes, remains a challenging task. Through comprehensive density functional calculations, we disentangle the relationship between the cathode potential and the ionicity of $TM-O$ bonds in $O3$ $NaTMO_2$ compounds in which TM ions is a fourth- or fifth-row transition metal. We demonstrate that the magnetic exchange interaction and the local distortions in the coordination environment of TM ions play more significant roles in determining the cathode potential of the $TM^{3+}$ $\to$ $TM^{4+}+ …
Representative compounds of the new family of magnetic materials Gd5-xNdxSi4 were analyzed by X-ray diffraction at the XRD1 beamline at LNLS. To reduce X-ray absorption, thin layers of the powder samples were mounted outside the capillaries and measured in Debye-Scherrer geometry as usual. The X-ray diffraction analyses and the magnetometry results indicate that the behavior of the magnetic transition temperature as a function of Nd content may be directly related to the average of the four smallest interatomic distances between different rare earth sites of the majority phase of each compound…
Simulation of spectra of x-ray absorption spectroscopy (XAS) at the L-edge is a well-established and reliable computational tool that, in combination with experimental measurements, reveals details about the local electronic structure and the chemical environment of transition metal ions (TMI). For light TMIs, model 2p XAS model Hamiltonian approaches (MHA) are fast and accurate in computing spectra. Here, an alternative method using artificial neural networks (ANN) is employed. The new approach predicts x-ray absorption spectra at the L-edge of light transition metals ions for elements from T…
Selecting nanocomposites for photonic switching applications requires optimizing their thermal, nonlinear and two-photon absorption characteristics. We simplify this step by defining a compound figure of merit (FOM_{C}) for nanocomposites of noble metals in dielectric based on criteria that limit these structures in photonic applications, i.e. thermal heating and two-photon absorption. The device independent results predict extremely large values of FOM_{C} for a specific combination of the metal and insulator dielectric constant given by ε_{h}=\frac{ε_{1}-ε_{2}}{2}, where ε_{h} is the dielect…
We develop a first-principles scheme based on the continued fraction approach an d ultrasoft pseudopotentials to calculate K-edge X-ray absorption spectra in solids. The method allows for calculations of K-edge X-ray absorption spectra in transition metal and rare-earths compounds with substantially reduced cutoffs respect to the norm-conserving case. We validate the method by calculating Si and O K-edges in $α$ quartz, Cu K-edge in Copper and in La$_2$CuO$_4$. For the case of Si and O edges in $α$ quartz and in Copper we obtain a good agreement with experimental data. In the Cu K-edge spectra…
The high pressure phase diagram of CsC8 graphite intercalated compound has been investigated at ambient temperature up to 32 GPa. Combining X-ray and neutron diffraction, Raman and X- ray absorption spectroscopies, we report for the first time that CsC8, when pressurized, undergoes phase transitions around 2.0, 4.8 and 8 GPa. Possible candidate lattice structures and the transition mechanism involved are proposed. We show that the observed transitions involve the structural re- arrangement in the Cs sub-network while the distance between the graphitic layers is continuously reduced at least up…
The number of absorption and Raman optical modes for each Wyckoff orbit in the high-temperature tetragonal (I4/mmm) parent lattice of the Ruddlesden-Popper compounds Ca$_3$X$_2$O$_7$, with X=Mn or X=Ti is given. We analyze the effect of sequential perturbations which lower the symmetry to Cmcm and Cmc2$_1$ and finally include magnetic ordering. We determine the power law behavior (within mean field theory) for the cross section for photon absorption and Raman scattering of modes which appear as the symmetry is successively lowered. In the Cmc2$_1$ phase we give a symmetry analysis to discuss t…
The effect of pressure on the optical-absorption edge of CdIn2S4, MgIn2S4, and MnIn2S4 thiospinels at room temperature is investigated up to 20 GPa. The pressure dependence of their band-gaps has been analyzed using the Urbach rule. We have found that, within the pressure-range of stability of the low-pressure spinel phase, the band-gap of CdIn2S4 and MgIn2S4 exhibits a linear blue-shift with pressure, whereas the band-gap of MnIn2S4 exhibits a pronounced non-linear shift. In addition, an abrupt decrease of the band-gap energies occurs in the three compounds at pressures of 10 GPa, 8.5 GPa, an…
A new ternary intermetallic compound, namely, YbMn2Sb2, has been synthesized and its magnetic and electrical transport properties have been studied in the temperature range of 2 to 300 K. This compound crystallizes in a trigonal, La2O2S type structure (space group P3bm1, No. 164) and is found to be ferromagnetically ordered at room temperature. The magnetism is attributed to the ordering of Mn sublattice. M5 xray absorption spectrum of YbMn2Sb2 obtained at room temperature suggests that the valency of Yb in this compound is close to 2. Electrical resistivity of this compound is metal like and …
Recent Progress in Ultrafast Dynamics of Transition-Metal Compounds Studied by Time-Resolved X-ray Techniques
University of Hyogo（兵库大学）；Osaka University（大阪大学）；National Institutes for Quantum Science and Technology（量子科学技术研究开发机构）；Japan Synchrotron Radiation Research Institute（日本同步辐射研究机构）
The Fe K X-ray absorption near edge structure (XANES) of BaFe2-xCoxAs2 superconductors was investigated. No appreciable alteration in shape or energy position of this edge was observed with Co substitution. This result provides experimental support to previous ab initio calculations in which the extra Co electron is concentrated at the substitute site and do not change the electronic occupation of the Fe ions. Superconductivity may emerge due to bonding modifications induced by the substitute atom that weakens the spin-density-wave ground state by reducing the Fe local moments and/or increasin…
The short-range organization around Ni atoms in orthorhombic $R$NiO$_{3}$ ($R$=Pr,Nd,Eu) perovskites has been studied over a wide temperature range by Ni K-edge x-ray absorption spectroscopy. Our results demonstrate that two different Ni sites, with different average Ni-O bond lengths, coexist in those orthorhombic compounds and that important modifications in the Ni nearest neighbors environment take place across the metal-insulator transition. We report evidences for the existence of short-range charge-order in the insulating state, as found in the monoclinic compounds. Moreover, our results…
InAs_{x}Sb_{1-x} alloys show a strong bowing in the energy gap, the energy gap of the alloy can be less than the gap of the two parent compounds. We demonstrate that a consequence of this alloying is a systematic degradation in the sharpness of the absorption edge. The alloy disorder induced band-tail (Urbach tail) characteristics are quantitatively studied for InAs_{0.05}Sb_{0.95}.
Ga2SeTe2 belongs to a family of materials with large intrinsic vacancy concentrations that are being actively studied due to their potential for diverse applications that include thermoelectrics and phase-change memory. In this article, the Ga2SeTe2 structure is investigated via synchrotron x-ray diffraction, electron microscopy, and x-ray absorption experiments. Diffraction and microscopy measurements showed that the extent of vacancy ordering in Ga2SeTe2 is highly dependent on thermal annealing. It is posited that stoichiometric vacancies play a role in local atomic distortions in Ga2SeTe2 (…
Mixed-valence compound Pb3O4 (minium) has been studied using X-ray absorption near-edge structure (XANES) spectroscopy and DFT calculations. In spite of presence of two valence states of lead [Pb(II) and Pb(IV)], the XANES spectrum of studied system is corresponding to apparently unified, an intermediate valence state of Pb. On the other hand, the 207Pb NMR spectra definitely show two different spectral bands corresponding to different Pb2+ and Pb4+ ions in Pb3O4 crystal structure. The explanation of this contradiction is related to the basics of XANES and NMR spectroscopy.
Quasiparticle spectra of potentially half-metallic Co2MnSi and Co2FeSi Heusler compounds have been calculated within the one-shot GW approximation in an all-electron framework without adjustable parameters. For Co2FeSi the many-body corrections are crucial: a pseudogap opens and good agreement of the magnetic moment with experiment is obtained. Otherwise, however, the changes with respect to the density-functional-theory starting point are moderate. For both cases we find that photoemission and x-ray absorption spectra are well described by the calculations. By comparison with the GW density o…
Kesterite I$_2$-II-IV-V$_4$ semiconductors are promising solar absorbers for photovoltaics applications. The band gap and it's character, either direct or indirect, are fundamental properties determining photovoltaic-device efficiency. We use a combination of accurate first-principles calculations and machine learning to predict the properties of the band gap for a large number of kesterite I$_2$-II-IV-V$_4$ semiconductors. In determining the magnitude of the fundamental gap, we compare results for a number of machine-learning models, and achieve a root mean squared error as low as 283 meV; th…
Infrared reflectance of alpha'-NaV2O5 single crystals in the frequency range from 50 cm-1 to 10000 cm-1 was studied for a, b and c-polarisations. In addition to phonon modes identification, for the a-polarised spectrum a broad continuum absorption in the range of 1D magnetic excitation energies was found. The strong near-IR absorption band at 0.8 eV shows a strong anisotropy with vanishing intensity in c-polarisation. Activation of new phonons due to the lattice dimerisation were detected below 35K as well as pretransitional structural fluctuations up to 65K.
The effect of external pressure on the magnetic properties and magnetocaloric effect of R(Co1-xSix)2 [R= Er, Dy and x=0, 0.025 and 0.05] compounds has been studied. The ordering temperatures of both the parent as well as the Si substituted compounds are found to decrease with pressure. In all the compounds, the critical field for metamagnetic transition increases with pressure. It is seen that the magnetocaloric effect in the parent compounds is almost insensitive to pressure, while there is considerable enhancement in the case of Si substituted compounds. Spin fluctuations arising due to the …
We present a comparative study of the optical properties - reflectance, transmission and optical conductivity - and Raman spectra of two layered bismuth-tellurohalides BiTeBr and BiTeCl at 300 K and 5 K, for light polarized in the a-b planes. Despite different space groups, the optical properties of the two compounds are very similar. Both materials are doped semiconductors, with the absorption edge above the optical gap which is lower in BiTeBr (0.62 eV) than in BiTeCl (0.77 eV). The same Rashba splitting is observed in the two materials. A non-Drude free carrier contribution in the optical c…
X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) were used to probe the oxidation state and element specific magnetic moments of Mn in Heusler compounds with different crystallographic structure. The results were compared with theoretical calculations, and it was found that in full Heusler alloys, Mn is metallic (oxidation state near 0) on both sublattices. The magnetic moment is large and localized when octahedrally coordinated by the main group element, consistent with previous theoretical work, and reduced when the main group coordination is tetrahedral. By c…
We report on the hydrogen sorption investigation of the mixed alkali cluster intercalated fulleride series NaxLi6-xC60. These compounds are isostructural to Na6C60 and Li6C60 while the cubic lattice parameter is linearly dependent on x. The H2 absorption/desorption was studied by means of charge/discharge kinetic and coupled calorimetric - manometric measurements. By varying the stoichiometry, we found the best compromise between absorption rate, temperature and amount of hydrogen in Na1Li5C60. This system is able to reversibly absorb up to 4.3 wt% H2 at 280 °C, which is 70 °C lower in tempera…
The structural, electronic, optical and thermodynamic properties of Mo2Ga2C are investigated using density functional theory (DFT) within the generalized gradient approximation (GGA). The optimized crystal structure is obtained and the lattice parameters are compared with available experimental data. The electronic density of states (DOS) is calculated and analyzed. The metallic behavior for the compound is confirmed and the value of DOS at Fermi level is 4.2 states per unit cell per eV. Technologically important optical parameters (e.g., dielectric function, refractive index, absorption coeff…
We present a detailed density functional theory based calculations of the structural, elastic, lattice dynamical, thermophysical, and optoelectronic properties of ternary semiconductors CaZn$_2$X$_2$ (X = N, P, As) in this paper. The obtained lattice parameters are in excellent agreement with the experimental values and other theoretical findings. These elastic constants satisfy the mechanical stability criteria. Moreover, many thermophysical parameters of these compounds are estimated, including the Debye temperature, average sound velocity, melting temperature, heat capacity, lattice thermal…
The density functional theory with generalized gradient approximation has been used to investigate the electronic structure of gadolinium pyrochlore A2Zr2O7 (A=Gd, Nd) ceramic synthesized in polycrystalline form by solid state reaction. Structural characterization of the compound was done through X-ray diffraction (XRD) followed by Rietveld analysis of the XRD pattern. The Zr-K edge X-ray absorption (XAFS) spectra of A2Zr2O7 (A=Gd, Nd) were analysed together with those Zr-foil, which was used as reference compounds. X-ray photoemission spectroscopy (XPS), X-ray absorption near edge structure (…
In this work the electronic properties of Fe doped CuO thin films are studied by using a standard density functional theory. This approach is based on the abinitio calculations under the Korringa Kohn Rostoker coherent potential approximation. We carried out our investigations in the framework of the general gradient approximation and self interaction corrected. The density of states in the energy diagrams are presented and discussed. The computed electronic properties of the studied compound confirm the half metalicity nature of this material. In addition, the absorption spectra of the studie…
Structural, elastic, electronic and optical properties of laves phase intermetallic compounds CaRh2 and LaRh2 prototype with MgCu2 are investigated by using the first principle calculations. These calculations stand on density functional theory (DFT) from CASTEP code. The calculated lattice parameters are consistent with the experimental values. The significant elastic properties, like as bulk modulus, shear modulus, Youngs modulus and the Poissons ratio are determined by applying the Voigt Reuss Hill (VRH) approximation. The analysis of Pughs ratio shows the ductile nature of both the phases.…
A comprehensive study of the structural, electronic, and optical properties of lead-free perovskites has been carried out by means of first principles method based on DFT. The calculations are performed for the compound of the type A2BX6 with A=Rb, and Cs; B=Sn, Pd, and Pt; and X=Cl, Br, and I. The calculated structural parameters (lattice constants and bond lengths) agree well with the experiments. The computed band gap reveals a semiconducting profile for all these compounds showing a decreasing trend of the band gap energy by changing the halide ions consecutively from Cl to Br and Br to I.…
The structural, electronic and optical properties of cubic double perovskite BaCoWO6 have been studied. Neutron powder diffraction data is collected on this sample from 6K to 300K. The crystal structure is face centered cubic, space group being Fm3m (No. 225). We did not find evidence for long range magnetic ordering in this system in this temperature range. The band-gap is estimated using Uv-vis spectroscopy. The Co-K edge X-ray absorption (XAFS) spectra of Ba2CoWO6 was analysed together with those Co-foil, which was used as reference compounds. X-ray photoemission spectroscopy (XPS), X-ray a…
Magnetic properties of DyAl$_{0.926}$Cr$_{0.074}$O$_3$ and DyAlO$_3$ were studied. We found that both compounds are antiferromagnetic with a low Néel transition temperature. At higher temperatures the magnetic characteristics show a Curie-Weiss dependence. The Néel temperature disappears when a field of about 2 T is applied, the system changes from an antiferromagnetic to a weak ferromagnetic behavior due to a metamagnetic transition. Furthermore, AC magnetic measurements in the Cr doped compound, at different frequencies, show a spin glass-like behavior. These transitions were studied and cor…
The structural electronic and optical properties of intermetallic compound MgRh were investigated by using the ab-initio technique from CASTEP code. In this study we have carried out the pseudo-potential plane-wave (PP-PW) method based on the density functional theory (DFT), within the generalized gradient approximation (GGA). Our calculated structural parameters and corresponding graphical values fit with other previous available experimental data and other theoretical observations. The calculated electronic band structure reveals metallic conductivity and the major contribution comes from Rh…
We establish a correlation between the internal stress in InN epilayers and their optical properties such as the measured absorption band edge and photoluminescence emission wavelength. By a careful evaluation of the lattice constants of InN epilayers grown on c-plane sapphire substrates under various conditions by metalorganic vapor phase epitaxy we find that the films are under primarily hydrostatic stress. This results in a shift in the band edge to higher energy. The effect is significant, and may be responsible for some of the variations in InN bandgap reported in the literature.
First-principles calculations using the plane-wave pseudopotential method within the generalized gradient approximation method were performed to study the pressure dependence of the structural, elastic, electronic and optical properties for the half-Heusler compounds ScPtSb and YPtSb in a cubic MgAgAs-type structure. The calculations were performed with the inclusion of spin-orbit coupling. The calculated equilibrium lattice parameters are in good agreement with the available experimental and theoretical values. The crystal rigidity and mechanical stability were discussed using the elastic con…
First-principles prediction of energy band gaps in 18-valence electron semiconducting half-Heusler compounds: Exploring the role of exchange and correlation
We report the structural, mechanical, electronic, optical, thermoelectric properties and spectroscopic limited maximum efficiency (SLME) of oxide double perovskite structure Ba2SbNbO6 and Ba2SbTaO6 compounds. All the investigations were performed through the first-principles density functional theory (DFT). The obtained values for the elastic constants reveal the mechanical stability of the studied compounds. The calculated data of bulk modulus (B), shear modulus (G), and Young's modulus (E) for Ba2SbTaO6 are found to be greater than those of Ba2SbNbO6. The ratio of Bulk to shear ratio (B/G) s…
A theoretical study of Mo2TiAlC2 compound belonging to the MAX phases has been performed by using the firstprinciples pseudopotential plane-wave method within the generalized gradient approximation. We have calculated the structural, elastic, electronic and optical properties of Mo2TiAlC2. To confirm mechanical stability, the elastic constants Cij are calculated. Other elastic parameters such as bulk modulus, shear modulus, compressibility, Young modulus, anisotropic factor, Pugh ratio, Poisson ratio are also calculated. The energy band structure and density of states are calculated and analyz…
Structural stability, electronic band structure, and optoelectronic properties of quaternary chalcogenide CuZn2MS4 (M =In and Ga) compounds via first principles
The three-dimensional ternary LiFeO2 compound presents various unusual essential properties. The main features are thoroughly explored by the density functional and many-body perturbation theory. The concise physical/chemical picture, the critical spin-polarizations and orbital hybridizations in the Li-O and Fe-O bonds, are clearly examined through geometric optimization, quasi-particle energy spectra, spin-polarized density of states, the spatial charge densities, the spin-density distributions, and the strong optical responses. The unusual optical transitions cover various frequency-dependen…
First-principles insights into the optoelectronic and thermoelectric properties of X3NbY4(X= Cu, Ag, Au; Y=S, Se, Te) sulvanite compounds for energy applications
Effect of Niobium Doping on the Crystal Structure and Hydrogen Sorption Properties of TiFe: Combined Synchrotron X-ray Diffraction and Extended X-ray Absorption Fine Structure Study
University of Stavanger（斯塔万格大学）；Institute for Energy Technology（能源技术研究所）
We present measurements of pure spin current absorption on lateral spin valves. By varying the width of the absorber we demonstrate that spin current absorption measurements enable to characterize efficiently the spin transport properties of ferromagnetic elements. The analytical model used to describe the measurement takes into account the polarization of the absorber. The analysis of the measurements allows thus determining the polarization and the spin diffusion length of a studied material independently, contrarily to most experiments based on lateral spin valves where those values are ent…
We investigate the rare-earth polychalcogenide $R_2$Te$_5$ ($R$=Nd, Sm and Gd) charge-density-wave (CDW) compounds by optical methods. From the absorption spectrum we extract the excitation energy of the CDW gap and estimate the fraction of the Fermi surface which is gapped by the formation of the CDW condensate. In analogy to previous findings on the related $R$Te$_n$ (n=2 and 3) families, we establish the progressive closing of the CDW gap and the moderate enhancement of the metallic component upon chemically compressing the lattice.
A simple user-friendly software named PRISA has been developed to determine optical constants (refractive index and extinction co-efficient), dispersion parameters (oscillator energy and dispersion energy), absorption co-efficient, band gap and thickness of semiconductor and dielectric thin films from their measured transmission spectrum, only. The thickness, refractive index, and extinction co-efficient of the films have been derived using Envelope method proposed by Swanepoel. The absorption co-efficient in the strong absorption region is calculated using the method proposed by Connel and Le…
We study the spin-dependent electronic structure of UTe and UT_{2}Si_{2} (T=Cu and Mn) compounds with a combination of x-ray magnetic circular dichroism measurements and first principle calculations. By exploiting the presence of sizable quadrupolar and dipolar contributions to the U L_{2,3}-edge x-ray absorption cross section we are able to provide unique information on the extent of hybridization between 5f and 6d/3d electronic states, a key parameter regulating the physical properties of all actinide materials. Since this information is hardly accessible to other probes, the new methodology…
A very simple method for determining the center (isomer) shift, CS, and the spectral area, A, of a Mössbauer spectrum is outlined. Its applicability is demonstrated in two examples viz. pyrite and a ternary sigma-phase Fe-Cr-Ni compound. Sets of the spectra recorded in the temperature interval of 78-295 K for the former, and 78-295 K for the latter were analyzed with the simple and a standard method. CS(T)- and A(T)-data obtained with both ways of the spectra analysis were analyzed in terms of the Debye model. The determined values of the Debye temperatures agree well within the error limit wi…
