Optical investigation of charge-transfer transitions in spinel Co3O4

Optical transitions in normal-spinel Co₃O₄ have been identified by investigating the variation of its optical absorption spectrum with the replacement of Co by Zn. Three optical-transition structures were located at about 1.65, 2.4, and 2.8 eV from the measured dielectric function of Co₃O₄ by spectroscopic ellipsometry. The variation of the absorption structures with the Zn substitution (Zn_xCo_3−xO₄) can be explained in terms of charge-transfer transitions involving d states of Co ions. The 1.65 eV structure is assigned to a d-d charge-transfer transition between the t_2g states of octahedral Co³⁺ ion and t₂ states of tetrahedral Co²⁺ ion, t_2g(Co³⁺)→t₂(Co²⁺). The 2.4 and 2.8 eV structures are interpreted as due to charge-transfer transitions involving the p states of O²⁻ ion: p(O²⁻)→t₂(Co²⁺) for the 2.4 eV absorption and p(O²⁻)→e_g(Co³⁺) for the 2.8 eV absorption. The observed gradual reduction of the 1.65 and 2.4 eV absorption strength with the increase of the Zn composition for Zn_xCo_3−xO₄ can be explained in terms of the substitution of the tetrahedral Co²⁺ sites by Zn²⁺ ions. The crystal-field splitting Δ_Oh between the e_g and the t_2g states of the octahedral Co³⁺ ion is estimated to be 2 eV.     

Synthesis and physical properties of mixed Co3O4/CoO nanorods by microwave hydrothermal technique

A mixture of crystalline Co₃O₄/CoO nanorods with non-uniform dense distribution has been successfully synthesized by microwave hydrothermal technique. The synthesized nanorods have been characterized by several techniques such as X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDX), and Fourier transforms infrared spectroscopy (FT-IR). The results showed that the as synthesized specimens contained mixed crystalline Co₃O₄/CoO nanorods with an average length of around 80 nm and an average diameter of 42 nm. UV–Vis spectrum of the nanorods exhibited a strong UV emission. The band energy gap of the product was 1.79 eV which lies between the energy gap of CoO and that for Co₃O₄. The obtained carrier concentration is of the order 4.32 × 10²⁷ m⁻³ and the dielectric constant is found to be 4.89. The electrical conductivity increases with increasing temperature and behaves as a semiconducting material with an activation energy of a bout 0.26 eV. This makes the as synthesized mixed Co₃O₄/CoO nanorods very useful for supercapacitor devices application. Magnetic hysteresis loops at room temperature of the as synthesized mixed oxides (Co₃O₄/CoO) nanorods exhibit typical soft magnetic behavior.     

X-ray photoelectron spectroscopy of Co3O4, Fe3O4, Mn3O4, and related compounds

The metal 2p region spectra of the mixed valence spinels, Co₃O₄, Fe₃O₄, Mn₃O₄, and related compounds were studied. The satellite splittings of Co 2p_{$\text{3}\text{2}$} for the octahedrally coordinated cobaltous ions are 6.2 eV and those for the tetrahedrally coordinated ones are about 5.3 eV. The Co 2p spectrum for Co₃O₄ is considered to be the sum of spectra of magnetic cobaltous ions and low-spin cobaltic ions. In the cases of Fe₃O₄ and Mn₃O₄, the oxidation states were not clearly distinguished because both the divalent and trivalent ions of iron and manganese are high-spin.     

Electronic structures of MRhO2, MRh2O4, RhMO4 and Rh2MO6 on the basis of X-ray spectroscopy and ESCA data

X-ray O Kα, Rh Mγ and a series of M Lα emission spectra, ESCA spectra of the valence and inner levels, and O K and Rh M_III quantum-yield spectra for X-ray photoemission of the rhodium double oxides MRhO₂ (M = Li, Na, K), MRh₂ O₄ (M = Be, Mg, Ca, Sr, Ba, Co, Ni, Cu, Zn, Cd, Pb), RhMO₄ (M = V, Nb, Ta) and Rh₂MO₆ (M = Mo, W) have been measured and the dependence of electronic structure on the metal M analysed. For all compounds the inner part of the valence band corresponds to O 2p_σ + O 2p_π + Rh 4d states, while the outer part corresponds to Rh 4d. The valence band is separated from the conduction band by a narrow gap of width less than 1 eV. The first empty band, near the bottom of the conduction band, is formed by Rh 4d states, followed by a band due to vacant O 2p states.     

Vacuum ultraviolet reflectivity of crystalline LaF3 and PrF3

The reflectivity of single crystals of LaF₃ and PrF₃ has been measured using synchrotron radiation. Transitions of the types Pr 4f-5d, fluorine 2p-conduction band and lanthanide 5p-conduction band have been identified. The latter give rise to a number of sharp peaks in the 20–25 eV region which may be excitonic in origin.     

Valence band photoemission spectroscopy of a ternary layered semiconductor: ZnIn2S4

UV photoemission spectroscopy (UPS) experiments have been carried out on the layer compound ZnIn₂S₄ employing several different photon energies in the range $\text{h}\text{?}{}_{\mathrm{\omega }}\text{= 9.5?21.2}\text{eV}$. The energy distribution curves (EDC's) exhibit four valence band density of states structures besides the Zn 3d peak. These five peaks appear 0.90 eV, 1.6 eV, 4.3 eV, 5.8 eV and 8.7 eV respectively below the top of the valence band, E_v. The atomic orbital character of the shallowest peak A appears different from that of the three deeper valence band peaks B, C and D and this is discussed in terms of the more or less pronounced ionic character of the intralayer chemical bonds. These results demonstrate that an overall understanding of the electronic states in complex structures can be achieved by an approach based on photoemission experiments and chemical bonding considerations which has been widely used in the past to study simple binary layer compounds.     

Valence band structure of single crystal titanium carbide,studied by soft X-ray and ultraviolet photoelectron spectroscopy

Valence states of single crystal titatium carbide (TiC_x, X?0.88) have been studied with photon energies ranging from far ultraviolet (u.v.) to soft X-ray. The valence band consists of two peaks located at 3 and 10 eV below the Fermi level. This is in good agreement with recent APW band structure calculations that predict a strong hybridization of the Ti 3d and C 2p bands and a C 2s band at lower energy.     

Small polaron migration in LixMn2O4: From first principles calculations

Migration of small polarons in λ-MnO₂, Li_0.5Mn₂O₄ and LiMn₂O₄ is studied via first principles calculations. Migration energy barriers of single small polaron migrations in λ-MnO₂, Li_0.5Mn₂O₄ and LiMn₂O₄ are 0.22 eV, 0.45 eV and 0.35 eV, respectively. The energy level changes of Mn-3d states along the polaron migration path are analyzed in detail. Results indicate that the activation energy barrier of polaron migration is strongly associated with the energy level shift of Mn-3dz² orbital, which is dependent on the short range structural arrangement of Mn³⁺/Mn⁴⁺ in the crystal. The electrical conduction properties of Li_xMn₂O₄ at room temperature are then discussed.     

Photoemission studies of single crystals of titanium carbide

The electron distribution in the valence band from single crystals of titanium carbide has been studied by photoelectron spectroscopy with photon energies h?ω = 16.8, 21.2, 40.8 and 1486.6 eV. The most conspicious feature of the electron distribution curves for TiC is a hybridization between the titanium 3d and carbon 2p states at ca. 3–4-eV binding energy, and a single carbon 2s band at ca. 10 eV. By taking into account the strong symmetry and energy dependence of the photoionization crosssections, as well as the surface sensitivity, we have identified strong emission from a carbon 2p band at ? 2.9-eV energy. Our results are compared with several recent energy band structure calculations and other experimental data. Results from pure titanium, which have been used for reference purposes, are also presented.The valence band from single crystals of titanium carbide have been studied by means of photoelectron spectroscopy, with photon energies ranging from 16.8 to 1486.6 eV.By taking into account effects such as the symmetry and energy dependence of the photoionization cross-sections and surface sensitivity, we have found the valence band of titanium carbide to consist of two peaks. The upper part of the valence band at 3–4 eV below the Fermi level consists of a hybridization between Ti 3d and C 2p states. The C 2p states observed in our spectra were mainly excited from a band about 2.9 eV below the Fermi level. The APW^5–9, MAPW¹⁰ and EPM¹¹ band structure calculations predict a flat band of p-character between the symmetry points X′₄ and K₃, most likely responsible for the majority of C 2p excitations observed. The C 2s states, on the other hand, form a single band centered around ?10.4 eV.The results obtained are consistent with several recent energy band structure calculations^{5–11, 13} that predict a combined bonding of covalent, ionic and metallic nature.     

Electronic structure of PbI2 from photoelectron spectra and the exciton problem

The valence band density of states for PbI₂ is determined from X-ray and u.v. induced photoelectron spectra. It is shown that the band derived from Pb 6s states is at 8 eV binding energy and not at the top of the valence bands as suggested by band structure and charge density calculations. A rigid shift in the predominantly iodine 5p derived bands to lower binding energy brings the band structure calculations into essential agreement with experiment. Pb 5d core level binding energies determined here are used to derive core level exciton energies of 0.7 eV from published reflectivity spectra.     

Isochromat spectroscopy on CePd3

Isochromat spectra from CePd₃ recorded at quantum energies of 9.7 and 72.7 eV are presented. The data obtained at 9.7 eV show three different peaks and are by and large identical to previously published data for a quantum energy of 1486 eV. Only two of those three peaks are present in the 72.7 eV spectrum. We conclude that the missing peak is bulk in origin and derives from a Ce5d-Pd4d hybridization leading to a Ce5d split off level from the filled Pd d-band.     

Electronic structure of the Sr2MgSi2O7:Eu persistent luminescence material

The electronic structures of the distrontium magnesium disilicate (Sr₂MgSi₂O₇(:Eu²⁺)) materials were studied by a combined experimental and theoretical approach. The UV-VUV synchrotron radiation was applied in the experimental study while the electronic structures were investigated theoretically by using the density functional theory. The structure of the valence and conduction bands and the band gap energy of the material as well as the position of the Eu²⁺ 4f ground state were calculated. The calculated band gap energy (6.7 eV) agrees well with the experimental value of 7.1 eV. The valence band consists mainly of the oxygen states and the bottom of the conduction band of the Sr states. The calculated occupied 4f ground state of Eu²⁺ lies in the energy gap of the host though the position depends strongly on the Coulomb repulsion strength. The position of the 4f ground state with respect to the valence and conduction bands is discussed using the theoretical and experimental evidence available.     

Electronic structure of Al2O3 from electron energy loss spectroscopy

The electronic structure of Al₂O₃ has been studied by electron energy loss spectroscopy (ELS), and an energy level model of both filled and empty states has been constructed from the ELS and available optical data. For the high temperature pyrolytic α-polycrystalline Al₂O₃ films, the transitions are assumed to originate at the two principal peaks in the valence band density of states and the O(2s) core state, and to terminate on two peaks within the conduction band density of states. We also report energy loss spectra due to excitations out of the deeper Al(2p), Al(2s), Al(1s), and O(1s) core levels. The excitations originating at the Al(2p), Al(2s), and Al(1s) core levels terminate on levels in the conduction band and on an exciton lying about 1 eV below the conduction-band edge.     

Valence and core state modifications in Pt3Ti

XPS data for the valence band, the Pt 4? states, and the Ti 2p states are presented for the intermetallic Pt₃Ti. Relative to the Pt valence band, the Pt₃Ti band shows a decrease in the density of states just below the Fermi level and a shift of the centroid to higher (binding) energy. Ti 2p and Pt 4? binding energies showed relatively large shifts with respect to the pure metals. These changes in the valence band density of states and core level binding energies are interpreted as arising from hybridization of the d-orbitals in both metals to form strong intermetallic bonds.     

A comparative study of a Heusler alloy Co2FeGe using LSDA and LSDA+U

We have calculated the on-site Coulomb repulsion (U) for the transition elements Co and Fe. To study the impact of Hubbard potential or on-site Coulomb repulsion (U) on structural and electronic properties the calculated values of U were added on GGA and LSDA. We performed the structure optimization of Co₂FeGe based on the generalized gradient approximation (GGA and GGA+U). The calculation of electronic structure was based on the full potential linear augmented plane wave (FP-LAPW) method and local spin density approximation (LSDA) as well as exchange correlation LSDA+U. The Heusler alloy Co₂FeGe fails to give the half-metallic ferromagnetism (HMF) when treated with LSDA. The LSDA+U gives a good result to prove that Co₂FeGe is a HMF with a large gap of 1.10 eV and the Fermi energy (E_F) lies at the middle of the gap of minority spin. The calculated density of states (DOS) and band structure show that Co₂FeGe is a HMF when treated with LSDA+U.     

Semiconducting properties and band structure of polycrystalline Bi4Mo20O62 compounds

Transport coefficient measurements (electrical conductivity, thermoelectric power and Hall effect) have been performed on compacted bars of Bi₄Mo₂₀O₆₂ in polycrystalline form over the temperature range (130–500 K) Experimental results are discussed in comparison to those obtained recently on Sb₄Mo₂₀O₆₂ They are interpreted on the basis of the same _p-type semiconductor model with two inverted deep levels near the midgap Conduction mechanisms are governed by acoustical-phonon scattering of the carrriers The top of the valence band is assumed to be formed from the d_xy orbitais of some of the Mo atoms leading to narrow bonding bands, while the donor and acceptor levels may be formed from the nonbonding d_xy orbitais of some of the Mo atoms of the distorted octahedron framework EPR measurements are discussed on the basis of this model and in comparison to the EPR results for Sb₄MO₂₀O₆₂ It is assumed that more than one narrow energy level (localized d states located below the valence band) contributes to the area of the line The XPS spectrum obtained on Bi₄Mo₂₀O₆₂ is also discussed.     

The thermoelectric power in the conductive phase of V6O13

The thermoelectric power of the high temperature conductive phase of V₆O₁₃ was measured and its variation with temperature is explained in terms of a simple model. The model assumes a narrow band for the d′ electrons and the Seebeck coefficient is calculated in the atomic limit of the narrow band. The only fitting parameter of the theoretical expression is U — the effective Coulomb repulsion between two electrons occupying the same site. Very good agreement between theory and experiment was obtained for U = 0.075 eV.     

Optical,thermal and polaron energy levels in α-Al2O3

Calculations of the thermal band gap, ionisation energy and O(2p) valence band width are reported based on defect lattice methods. From these it is estimated that the large polaron is the preferred hole state in α-Al₂O₃ by about 0.4 eV. Theoretical values for the optical and thermal energy levels of Ti³⁺ in α-Al₂O₃ are also reported.     

Charge-transfer transitions and optical spectra of chromites

Specific features of charge-transfer states and charge-transfer transitions of the O_2p → Cr_3d type in octahedral complexes (CrO₆)^9? have been considered in the cluster approximation. Reduced matrix elements of the electric-dipole moment operator on many-electron wave functions, which are the initial and final states for charge-transfer transitions, are calculated. The results are parameterized, and the relative intensities of different allowed charge-transfer transitions in the absence of mixing of different charge-transfer configurations with identical symmetry are calculated. This mixing is taken into account within the Tanabe-Sugano theory, and the true energies and intensities of many-electron charge-transfer transitions are obtained. The Coulomb interaction between 2p electrons of O^2? ligands and 3d electrons of the central Cr³⁺ ion in (CrO₆)^9? cluster is considered. The influence of this interaction on the optical spectra is found to be insignificant. Simulation of the optical spectra of chromium oxides has shown the presence of a band of complex charge-transfer transitions composed of 33 lines with a total width of about 8 eV. The model spectrum is in adequate agreement with the experimental data, which indicates limited applicability of the widespread view that charge-transfer transition spectra have a simple structure.