The electronic structure of CeO2 and PrO2

We have determined the electronic structure of CeO₂ and PrO₂ by performing SCF band calculations. We find that in both systems there are metal f- and d- electrons in the oxygen 2p bands. We discuss the question of valency and ionicity in these systems.     

Density functional theory study of doping effects in monoclinic clinobisvanite BiVO4

The doping effects of several transition metal impurities for monoclinic BiVO₄ are studied by DFT calculations. The results indicated that transition metal doping could reduce the effective mass of holes on the top of valence band, except Zr doping. In particular, we found the “e” states of impurities have significant influence on the photophysical properties of BiV_1 − xM_xO₄ under visible-light irradiation.     

Band structure calculations on the layered compounds FeGa2S4 and NiGa2S4

For the compounds FeGa₂S₄ and NiGa₂S₄ band structure calculations have been performed by the ab initio plane wave pseudo-potential method. The valence charge density distribution points to an ionic type of chemical bonding between the transition metal atoms and the ligand atoms. Two models for the pseudo-potentials are used to calculate the band structures: (a) only s and p electrons and (b) also the d-shells of the transition metal atoms are included in the pseudo-potentials. The differences between these two cases of band structures are discussed. Energy gap formation peculiarities are analysed for both crystals. Zak's elementary energy band concept is demonstrated for the energy spectra of the considered crystals.     

Density functional theory study of NO2-sensing mechanisms of pure and Ti-dopedWO3 （002） surfaces

Density functional theory (DFT) calculations are employed to explore the NO₂-sensing mechanisms of pure and Ti-doped WO₃ (002) surfaces. When Ti is doped into the WO₃ surface, two substitution models are considered: substitution of Ti for W_6c and substitution of Ti for W_5c. The results reveal that substitution of Ti for 5-fold W forms a stable doping structure, and doping induces some new electronic states in the band gap, which may lead to changes in the surface properties. Four top adsorption models of NO₂ on pure and Ti-doped WO₃ (002) surfaces are investigated: adsorptions on 5-fold W (Ti), on 6-fold W, on bridging oxygen, and on plane oxygen. The most stable and likely NO₂ adsorption structures are both N-end oriented to the surface bridge oxygen O_1c site. By comparing the adsorption energy and the electronic population, it is found that Ti doping can enhance the adsorption of NO₂, which theoretically proves the experimental observation that Ti doping can greatly increase the WO₃ gas sensor sensitivity to NO₂ gas.     

Structural and electronic properties of Fe-doped BaTiO3 and SrTiO3

We have performed first principles calculations of Fe-doped BaTiO3 and SrTiO3. Dopant formation energy, structure distortion, band structure and density of states have been computed. The dopant formation energy is found to be 6.8eV and 6.5eV for Fe-doped BaTiO3 and SrTiO3 respectively. The distances between Fe impurity and its nearest O atoms and between Fe atom and Ba or Sr atoms are smaller than those of the corresponding undoped bulk systems. The Fe defect energy band is obtained, which mainly originates from Fe 3d electrons. The band gap is still an indirect one after Fe doping for both BaTiO3 and SrWiO3, but the gap changes from Γ-R point to Γ-X point.     

Nitrogen doping concentration influence on NaNbO3 from first-principle calculations

The nitrogen concentration effects on electronic band structures and photocatalytic performance of N-doped sodium niobate (NaNbO₃) have been investigated by first-principles calculations based on density functional theory (DFT). At lower nitrogen doping levels, some localized N 2p states are formed above the valence band (O 2p) in N-doped NaNbO₃, leading to the reduction of the photon transition energy in comparison to that of undoped compound. Under higher doping levels, the N 2p states mix with O 2p states and then move the top of valence band upward. Two possible mechanisms for increasing visible light absorbance in N-doped NaNbO₃ are tentatively put forward according to the doping levels, which would be of importance in understanding and developing the visible-light-sensitive nitrogen-doped multimetal oxide.     

First-principles calculation of structural and electronic properties of pyrochlore Lu2Sn2O7

A Density functional theory method within generalized gradient approximation has been performed to obtain the static lattice parameters, oxygen positional parameter, bond length and bond angle and electronic properties of ideal Lu₂Sn₂O₇ pyrochlore. The results are in excellent agreement with available experimental measurements. Density of states (DOS) of this compound was presented and analysed. We also notice the presence of the hybridization between oxygen and Lu metal. The band structure calculations show that the compound has direct band gap of 2.67 eV at the Γ point in the Brillouin zone and this indicates that the material has a semi-conducting feature.     

Electronic structures and optical properties of rutile TiO2 with different point defects from DFT + U calculations

The electronic states and formation energies of four types of lattice point defects in rutile TiO₂ are studied using the first-principles calculations. The existence of oxygen vacancy leads to a deep donor defect level in the forbidden band, while the Ti interstitial forms two local states. It is predicted that oxygen vacancy prefers to combine with Ti-interstitial to form V_O–Ti_i dimer by a partial 3d electron transfer from the Ti_i to its neighboring V_O. The charge distribution between a Ti interstitial and its neighboring Ti ions partially shields the Coulomb interactions. Lastly, optical properties of these defective lattices are discussed.     

Effects of B′-site transition metal on the properties of double perovskites Sr2FeMO6 (M=Mo, W): B′ 4d-5d system

The crystal structure, magnetic and magnetotransport properties of the variation of B′-site transition metal in Sr₂FeMO₆ (M=Mo, W) with double perovskites structure have been investigated systematically. Measurements of magnetization vs. temperature at H=5 T show that Sr₂FeMoO₆ is a ferromagnet and Sr₂FeWO₆ is an antiferromagnet with T_N∼35 K. Additionally, the large magnetoresistance ratio (MR) of ∼22% (H=3 T) at room temperature (RT) was observed in the Sr₂FeWO₆ compound. However, the Sr₂FeMoO₆ compound did not show any significant MR even at high fields and RT (MR∼1%; H=3 T and 300 K). The implications of these findings are supported by band structure calculations to explain the interaction between the 4d(Mo) and 5d(W) orbitals of transition metal ions and oxygen ions.     

Understanding the Effects of Point Defects on the Electronic Properties of Titania Nanoparticles: An Ab Initio Study

First-principles calculations are used to study the electronic structure of the TiO₂(101) surface. The effect of oxygen vacancies and interstitial titanium ions on the electronic structure is investigated, and models for optical single-electron charge transfer transitions in the structure are proposed. We found that the addition of an uncharged oxygen vacancy leads to a shift of the total density of states toward lower energy, and the bandgap increases. Therefore, interstitial titanium ion incorporation induces donor states above the valence band and increases the bandgap. These results can be used to explain the observed blueshift in nanoscale TiO_2.     

First-principles study of La and Sb-doping effects onelectronic structure and optical properties of SrTiO3

The effects of La and Sb doping on the electronic structure and optical properties of SrTiO 3 are investigated by first-principles calculation of the plane wave ultra-soft pseudo-potential based on density functional theory. The calculated results reveal that corner-shared TiO 6 octahedra dominate the main electronic properties of SrTiO 3 , and its structural stability can be improved by La doping. The La 3+ ion fully acts as an electron donor in Sr 0.875 La 0.125 TiO 3 and the Fermi level shifts into the conduction bands (CBs) after La doping. As for SrSb 0.125 Ti 0.875 O 3 , there is a distortion near the bottom of the CBs for SrSb 0.125 Ti 0.875 O 3 after Sb doping and an incipient localization of some of the doped electrons trapped in the Ti site, making it impossible to describe the evolution of the density of states (DOS) within the rigid band model. At the same time, the DOSs of the two electron-doped systems shift towards low energies and the optical band gaps are broadened by about 0.4 and 0.6 eV for Sr0.875La0.125TiO3 and SrSb0.125Ti0.875O3 , respectively. Moreover, the transmittance of SrSb0.125Ti0.875O3 is as high as 95% in most of the visible region, which is higher than that of Sr0.875La0.125TiO3 (85%). The wide band gap, the small transition probability and the weak absorption due to the low partial density of states (PDOS) of impurity in the Fermi level result in the significant optical transparency of SrSb0.125 Ti0.875 O3 .     

Electronic structure and bonding in CaH2: Experiment and theory

Synchrotron radiation photoemission studies of Ca and CaH₂ reveal changes in the electronic structure and bonding which directly reflect metal-hydrogen interactions. The results indicate similarities between the saline dihydrides and the transition metal dihydrides, particularly the energy location and width of the bonding band states. Combined with APW band calculations for CaH₂ in the CaF₂ structure, they provide new insight regarding bonding in hydrides.     

First-principles study of electronic structures and optical properties of Cu, Ag, and Au-doped anatase TiO2

We perform first-principles calculations to investigate the band structure, density of states, optical absorption, and the imaginary part of dielectric function of Cu, Ag, and Au-doped anatase TiO₂ in 72 atoms systems. The electronic structure results show that the Cu incorporation can lead to the enhancement of d states near the uppermost of valence band, while the Ag and Au doping cause some new electronic states in band gap of TiO₂. Meanwhile, it is found that the visible optical absorptions of Cu, Ag, and Au-doped TiO₂, are observed by analyzing the results of optical properties, which locate in the region of 400-1000 nm. The absorption band edges of Cu, Ag, and Au-doped TiO₂ shift to the long wavelength region compared with the pure TiO₂. Furthermore, according to the calculated results, we propose the optical transition mechanisms of Cu, Ag, and Au-doped TiO₂. Our results show that the visible light response of TiO₂ can be modulated by substitutional doping of Cu, Ag, and Au.     

Defect formation and water incorporation in Y2O3

The molecular statics method is used to study the formation of defects and water incorporation in Y₂O₃. The crystal structure, the isothermal compressibility, and the formation enthalpy of Y₂O₃ calculated with the chosen interaction potentials are in good agreement with the experimental data. The formation energies of intrinsic and impurity defects are evaluated. The binding energy of protons and oxygen vacancies with an acceptor impurity at different distances is calculated. Various water incorporation reactions in the oxide are examined, including the mechanisms involving oxygen interstitial sites and oxygen vacancies produced by the acceptor doping. It is shown that the water incorporation in pure Y₂O₃ is energetically less favorable than in the acceptor doped oxide.     

Effect of indium doping on photoelectrochemical properties of Cd0.9Zn0.1Se photosensitive films

Indium doped Cd_0.9Zn_0.1Se films have been synthesized by chemical bath deposition method. The deposited films act as photoanode in photoelectrochemical (PEC) cells. The varying concentration of indium from 0.01 to 1.0 mol% was used. The film thickness increases from 0.72 to 0.80 μm as doping concentration increases up to 0.1 mol%, thereafter it decreases. The cell configuration is n-Cd_0.9Zn_0.1Se:In|NaOH (1 M)+S (1 M)+Na₂S (1 M)|C_(graphite). The various performance parameters were examined with respect to doping concentration of indium. It is found that fill factor and efficiency is maximum for 0.1 mol% indium photosensitive films. This is due to low resistance, high flat band potential, maximum open circuit voltage as well as maximum short-circuit current. The barrier height was examined from the temperature dependence of the reverse saturation current. The lighted ideality factor was found to be minimum for 0.1 mol% indium photosensitive films. A cell utilizing doping photosensitive films showed a wider spectral response. The utility of this work is in improving efficiency of the PEC cell.     

Electronic properties of anatase TiO2 doped by lanthanides: A DFT+U study

The effects of mono-doping of 4f lanthanides with and without oxygen vacancy defect on the electronic structures of anatase TiO₂ have been studied by first-principles calculations with DFT+U (DFT with Hubbard U correction) to treat the strong correlation of Ti 3d electrons and lanthanides 4f electrons. Our results revealed that dopant Ce is easy to incorporate into the TiO₂ host by substituting Ti due to its lower substitutional energy (∼−2.0 eV), but the band gap of the system almost keeps intact after doping. The Ce 4f states are located at the bottom of conduction band, which mainly originates from Ti 3d states. The magnetic moment of doped Ce disappears due to electron transfer from Ce to the nearest O atoms. For Pr and Gd doping, their substitutional energies are similar and close to zero, indicating that both of them may also incorporate into the TiO₂ host. For Pr doping, some 4f spin-down states are located next to the bottom of the conduction band and narrow the band gap of the doping system. However, for Gd doping, the 4f states are located in deep valence band and there is no intermediate band in the band gap. The magnetic moment of dopant Gd is close to the value of isolated Gd atom (∼7 μB), indicating no overlapping between Gd 4f with other orbitals. For Eu, it is hard to incorporate into the TiO₂ host due to its very higher substitutional energy. The results also indicated that oxygen vacancy defect may enhance the adsorption of the visible light in Ln-doped TiO₂ system.     

多自旋态离子Co替代诱导La2/3Ca1/3MnO3体系的输运反常

利用具有多自旋态的Co离子进行Mn位替代,制备了La_2/3Ca_1/3Mn_1-xCo_xO₃ (0≤x≤0.15) 系列样品并研究了体系的结构和输运特性.结果表明,在替代范围内,样品呈现很好的单相结构,各晶格参数随替代量的增大而减小;Co替代导致体系出现电输运反常,具体表现为在居里温度T_C以下电阻-温度曲线的二次金属-绝缘转 关键词： Mn位替代 双峰现象 自旋结构 磁电阻效应     

Surface properties of LiCoO2, LiNiO2 and LiNi1−xCoxO2

The surface composition and chemical environment of LiCoO₂, hexagonal LiNiO_2, cubic LiNiO₂, and the mixed transition metal oxide LiNi_0.5Co_0.5O₂ have been determined by Auger electron and X-ray photoelectron spectroscopies. While the LiCoO₂ surface properties can easily be extrapolated from bulk composition, the nickel-containing materials are less straightforward. Their surface concentration tends to be depleted in lithium relative to that of the bulk and shows an atypical chemical environment for the constituent elements. The Ni 2p XPS photoemission suggests a near “ NiO-like” selvedge through the XPS binding energies and satellite structure which are essentially identical to that of NiO; the spectrum appears fairly insensitive to lithium concentration. Although there is little evidence for higher binding energy Ni³⁺ species or for an electron poor Ni^2.δ+-derived band structure in the XPS, the lattice oxygen is very electron-rich and yields among the lowest binding energies reported for a transition metal oxide. The nickel-containing lithium oxide selvedge is thus not simply “NiO” and the surface lithium cations have a measurable effect on the electronic structure even in their more highly depleted levels. This is explained in the context of the charge-transfer model of the oxide band structure.     

Mg,Al掺杂对LiCoO2体系电子结构影响的第一原理研究

为了研究Mg, Al掺杂对锂二次电池正极材料LiCoO₂体系的电子结构的影响，进而揭示Mg掺杂的LiCoO₂具有高电导率的机理，对Li(Co, Al)O₂和Li(Co, Mg)O₂进行了基于密度泛函理论的第一原理研究. 通过对能带及态密度的分析，发现在Mg掺杂后价带出现电子态空穴，提高了电导，并且通过歧化效应（disproportionation）改变了Co-3d电子在各能级的分布，而Al掺杂则没有这些作用. O关键词： 2')" href="#">LiCoO₂ 电子结构 第一原理 电导     

Electronic Structure and Optical Properties of La-Doped SrTiO3 and Sr2TiO4 by Density Function Theory

The effect of La doping on the electronic structure and optical properties of SrTiO₃ and Sr₂TiO₄ is investigated by the first-principles calculation of plane wave ultrasoft pseudopotential based on the density function theory (DFT). The calculated results reveal that the electron doping in the case of Sr_0.875La_0.125TiO₃ and Sr_1.875La_0.125TiO₄ can be described within the rigid band model. The La³⁺ ions fully acts as electron donors in Sr_0.875La_0.125TiO₃ and Sr_1.875La_0.125TiO₄ systems and the Fermi level shifts further into the conduction bands (CBs) for Sr_1.875La_0.125TiO₄ compared to Sr_0.875La_0.125TiO₃. The two systems exhibit n-type degenerate semiconductor features. At the same time, the density of states (DOS) of the two systems shift towards low energies and the optical band gaps are broadened. The Sr_1.875La_0.125TiO₄ is highly transparent with the transmittance about 90% in the visible range, which is larger than that of Sr_0.875La_0.125TiO₃(85%). The wide band gap, small transition probability and weak absorption due to the low partial density of states (PDOS) of impurity in the Fermi level result in the optical transparency of the films...