Spectrum redshift effect of anatase TiO2 codoped with nitrogen and first transition elements

The electronic and optical properties, including band structure, density of states(DOS), absorption rate, refractive index, and dielectric function, of anatase TiO2 codoped with N and first transition elements are investigated using the plane wave pseudopotential method based on the density functional theory. The calculation results show that TiO2 codoping with N and first transition elements(Sc, V, Cr, Mn, and Fe) lead to significant reduction of conduction band relative to the Fermi level, reduction of band gap width, formation of new donor, and acceptor impurity levels below the conduction band and above the valence band, and cause some redshifts of optical absorption band edge with the amount of redshift decrease in the following order: N–Fe N–Cr N–Mn. Further, the synergistic effect of shallow donor and acceptor levels enhances light excitation for effective separation of electron–hole pairs and enhancement of light absorption ability, thereby increasing the TiO2 photocatalytic properties. This study reveals that the visible-light absorption ability of the codoped anatase TiO2 decreases in the order of N–Fe N–Cr N–Mn N–Sc N–V N, and does not monotonically follow the dopant atomic number. Especially, in N–Cr codoped TiO2, the 4s atomic orbit of Cr is not completely filled, which hybridized with the p electronic orbit most probably acts as photo-generated electron trap centers resulting in higher photocatalytic activity than that of N–Mn codoped TiO2.     

Effect of Microstructure of TiO2 Thin Films on Optical Band Gap Energy

TiO2 coatings are prepared on fused silica with conventional electron beam evaporation deposition. After annealed at different temperatures for four hours, the spectra and XRD patterns of TiO2 thin film are obtained. XRD patterns reveal that only anatase phase can be observed in TiO2 coatings regardless of the different annealing temperatures, and with the increasing annealing temperature, the grain size gradually increases. The relationship between the energy gap and microstructure of anatase is determined and discussed. The quantum confinement effect is observed that with the increasing grain size of TiO2 thin film, the band gap energy shifts from 3.4 eV to3.21 eV. Moreover, other possible influence of the TiO2 thin-film microstructure, such as surface roughness and thin film absorption, on band gap energy is also expected.     

Line intensities of the asymptotic asymmetric-top radical HO2 at high temperatures

The total internal partition sums were calculated in the product approximation at temperatures up to 5000 K for the asymptotic asymmetric-top HO2 molecule. The calculations of the rotational partition function and the vibrational partition function were carried out with the rigid-top model and in the harmonic oscillator approximation, respectively. Our values of the total internal partition sums are consistent with the data of HITRAN database with -0.14% at 296 K. Using the calculated partition functions, we have calculated the line intensities of υ2 band of HO2 at several high temperatures. The results showed that the calculated line intensities are in very good agreement with those of HITRAN database at temperatures up to 3000 K, which provides a strong support for the calculations of partition functions and line intensities at high temperatures. Then we have extended the calculation to higher temperatures. The simulated spectra of υ2 band of the asymptotic asymmetric-top HO2 molecule at 4000 and 5000 K are also obtained.     

Electronic Structures of the Filled Tetrahedral Semiconductor Li3AlN2

The first-principles total energy calculations with the local density approximation （LDA） and the plane wave pseudopotential method are employed to investigate the structural properties and electronic structures of Li3AlN2. The calculated lattice constants and internal coordination of atoms agree well with the experimental results. Detailed studies of the electronic structure and the charge-density redistribution reveal the features of the strong ionicity bonding of Al-N and Al-Li, and strong hybridizations between Li and N in Li3AlN2. Our band structure calculation verifies Li3AlN2 is a direct gap semiconductor with the LDA gap value of about 2.97eV and transition at Г.     

First-Principles Band Calculations on Electronic Structures of Ag-Doped Rutile and Anatase TiO2

The electronic structures of Ag-doped rutile and anatase Ti02 are studied by first-principles band calculations based on density functional theory with the full-potential linearized-augmented-plane-wave method. New occupied bands are found between the band gaps of both Ag-doped rutile and anatase TiO2. The formation of these new bands can be explained mainly by their orbitals of Ag 4d states mixed with Ti 3d states and are supposed to contribute to their visible light absorption.     

First-principles investigation of the electronic structure and magnetism of eskolaite

The electronic structure and magnetism of eskolaite are studied by using first-principles calculations where the on-site Coulomb interaction and the exchange interaction are taken into account and the LSDA+U method is used. The calculated energies of magnetic configurations are very well fitted by the Heisenberg Hamiltonian with interactions in five neighbour shells; interaction with two nearest neighbours is found to be dominant. The Néel temperature is calculated in the spin-3/2 pair-cluster approximation. It is found that the measurements are in good agreement with the calculations of lattice parameters, density of states, band gap, local magnetic moment, and the Néel temperature for the values of U and J that are close to those obtained within the constrained occupation method. The band gap is of the Mott--Hubbard type.     

Ab Initio Calculations for the BaTiO3 （001） Surface Structure

The ab initio method within the local density approximation is applied to calculate cubic BaTiO3 (001) surface relaxation and rumpling for two different terminations (BaO and TiO2 ). Our calculations demonstrate that cubic perovskite BaTiO3 crystals possess surface polarization, accompanied by the presence of the relevant electric field. We analyse their electronic structures (band structure, density of states and the electronic density redistribution with emphasis on the covalency effects). The results are also compared with that of the previous ab initio calculations. Considerable increases of Ti-O chemical bond covalency nearby the surface have been observed. The band gap reduces especially for the TiO2 termination.     

Optoelectronic and thermoelectric properties of Zintl YLi_3A_2(A = Sb,Bi) compounds through modified Becke-Johnson potential

In the present work,we investigate the structural,optoelectronic and thermoelectric properties of the YLi_3X_2(X = Sb,Bi) compounds using the full potential augmented plane wave plus local orbital(FP-APW+lo) method.The exchangecorrelation potential is treated with the generalized gradient approximation/local density approximation(GGA/LDA) and with the modified Becke-Johnson potential(TB-mBJ) in order to improve the electronic band structure calculations.In addition,the estimated ground state properties such as the lattice constants,external parameters,and bulk moduli agree well with the available experimental data.Our band structure calculations with GGA and LDA predict that both compounds have semimetallic behaviors.However,the band structure calculations with the GGA/TB-mBJ approximation indicate that the ground state of the YLi_3Sb_2 compound is semiconducting and has an estimated indirect band gap(Γ-L) of about 0.036 eV while the ground state of YLi_3Bi_2 compound is semimetallic.Conversely the LDA/TB-mBJ calculations indicate that both compounds exhibit semiconducting characters and have an indirect band gap(Γ-L) of about 0.15 eV and 0.081 eV for YLi_3Sb and YLi_3Bi_2 respectively.Additionally,the optical properties reveal strong responses of the herein materials in the energy range between the IR and extreme UV regions.Thermoelectric properties such as thermal conductivity,electrical conductivity,Seebeck coefficient,and thermo power factors are also calculated.     

Magnetic and Electronic Properties of Double Perovskite Ba_2SmNbO_6 without Octahedral Tilting by First Principle Calculations

The structural, magnetic and electronic properties of the double perovskite Ba_2 SmNbO_6(for the simple cubic structure where no octahedral tilting exists anymore) are studied using the density functional theory within the generalized gradient approximation as well as taking into account the on-site Coulomb repulsive interaction.The total energy, the spin magnetic moment, the band structure and the density of states are calculated. The optimization of the lattice constants is 8.5173 A, which is in good agreement with the experimental value 8.5180 A.The calculations reveal that Ba_2 SmNbO_6 has a stable ferromagnetic ground state and the spin magnetic moment per molecule is 5.00μB/f.u. which comes mostly from the Sm~(3+) ion only. By analysis of the band structure,the compound exhibits the direct band gap material and half-metallic ferromagnetic nature with 100% spin-up polarization, which implies potential applications of this new lanthanide compound in magneto-electronic and spintronic devices.     

Common electronic band gaps and similar optical properties of ZnO nanotubes

Electronic and optical properties of single-walled zinc oxide （ZnO） nanotubes are investigated from the firstprinciples calculations. Electronic structure calculations show that ZnO nanotubes are all direct band gap semiconducting nanotubes and the band gaps are relatively insensitive to the diameter and chirality of tubes. The origin of the common electronic band gaps of ZnO nanotubes is explained in terms of band-folding from the two-dimensional band structure of graphite-like sheet. Moreover, the optical properties such as dielectric function and energy loss function spectra of different ZnO nanotubes are very similar, relatively independent of diameter and chirality of tubes. The calculated dielectric function and loss function spectra show a moderate optical anisotropy with respect to light polarization.     

TiO2纳米管的力学和电子学性质

基于密度泛函理论研究了纤铁矿和锐钛矿型TiO₂纳米管的原子结构、稳定性、Young模量以及电子能带结构.计算结果显示：在纳米管直径较小时,锐钛矿型TiO₂纳米管的稳定性要好于纤铁矿型纳米管,随着管径的增大,纤铁矿型纳米管变得比锐钛矿型纳米管要更稳定.纤铁矿型TiO₂纳米管具有比锐钛矿型纳米管更大的Young模量,力学性能比较优异.另外,通过对电子能带结构的研究发现,手性对TiO₂纳米管的电子结构影响较大,纤铁矿（0,n）型和锐钛矿（n,0）型纳米管为间接带隙半导体,而纤铁矿（n,0）型和锐钛矿（0,n）型纳米管却具有直接带隙. 关键词： 2纳米管')" href="#">TiO₂纳米管 Young模量 间接带隙 直接带隙     

Optical properties of anatase and rutile TiO_2 studied by GGA + U

The optical properties of thermally annealed TiO_2 samples depend on their preparation process, and the TiO_2 thin films usually exist in the form of anatase or rutile or a mixture of the two phases. The electronic structures and optical properties of anatase and rutile TiO_2 are calculated by means of a first-principles generalized gradient approximation(GGA) +U approach. By introducing the Coulomb interactions on 3d orbitals of Ti atom(U~d) and 2p orbitals of O atom(U~p), we can reproduce the experimental values of the band gap. The optical properties of anatase and rutile TiO_2 are obtained by means of the GGA+U method, and the results are in good agreement with experiments and other theoretical data. Further, we present the comparison of the electronic structure, birefringence, and anisotropy between the two phases of TiO_2. Finally,the adaptability of the GGA+U approach has been discussed.     

Optical properties of anatase and rutile titanium dioxide: Ab initio calculations for pure and anion-doped material

The optical properties of rutile and anatase titanium dioxide (TiO₂) are calculated from the imaginary part of the dielectric function using pseudopotential density functional method within its generalized gradient approximation (GGA) and a scissors approximation. The fundamental absorption edges calculated for the unit cell of both rutile and anatase are consistent with experimentally reported results of single crystal rutile and anatase TiO₂ and with previous theoretical calculations. A significant optical anisotropy is observed in the anatase structure which holds promise for investigating the band gap modification with better visible-light response and provides a reliable foundation for addressing the effect of impurities on the fundamental absorption edge/band gap of anatase TiO₂. Further calculations on the electronic structure and the optical properties of C-, N-, and S-doped anatase TiO₂ are performed. The results are analyzed and discussed in terms of optical anisotropy and scissors approximations.     

Si掺杂锐钛矿TiO2的第一性原理研究

为了研究Si掺杂对锐钛矿TiO2的电子蛄构和光催化性能的影响,利用基于第一性原理的密度泛函理论计算了纯TiO2及Si掺杂TiO2的杂质形成能、能带结构及态密度.研究蛄果表明,Si的掺杂位置与制备条件有关,富钛和富氧条件下,Si最容易代替TiO2中Ti的位置.几何优化后Si掺杂TiO2超晶胞的晶格参数和晶胞体积都发生一定...     

Electronic Structure and Visible-Light Absorption of Transition Metals(TM=Cr,Mn, Fe,Co) and Zn-Codoped SrTiO_3: a First-Principles Study

First-principles calculations are performed on the influence of transition metal(TM=Cr, Mn, Fe, Co) as codopants on the electronic structure and visible-light absorption of Zn-doped Sr TiO_3. The calculated results show that(Zn,Mn)-codoped Sr TiO_3 requires the smallest formation energy in four codoping systems. The structures of the codoped systems display obvious lattice distortion, inducing a phase transition from cubic to rhombohedral after codoping. Some impurity Cr, Mn and Co 3d states appear below the bottom of conduction band and some Fe 3d states are located above the top of valence band, which leads to a significant narrowing of band gap after transition metal codoping. The enhancement of visible-light absorption are observed in transition metals(TM=Cr, Mn, Fe, Co) and Zn codoped Sr TiO_3 systems. The prediction calculations suggested that the(Zn,Mn)-and(Zn,Co)-codoped SrTiO_3 could be the desirable visible-light photocatalysts.     

Synthesis of Different TiO_2 Nanostructures and Their Physical Properties

Titanium dioxide(TiO_2) nanosheet, nanorod and nanotubes are synthesized using chemical vapor deposition(CVD) and anodizing processes. TiO_2 nanosheets are grown on Ti foil which is coated with Au catalyst in CVD,TiO_2 nanorods are synthesized on treated Ti foil with HCI by CVD, and TiO_2 nanotubes are prepared by the three-step anodization method. Scanning electron microscopy shows the final TiO_2 structures prepared using three processes with three different morphologies of nanosheet, nanorod and nanotube. X-ray diffraction verifies the presence of TiO_2. TiO_2 sheets and rods are crystalized in rutile phase, and TiO_2 tubes after annealing turn into the anatase crystal phase. The optical investigations carried out by diffuse reflection spectroscopy reveal that the morphology of TiO_2 nanostructures influencing their optical response and band gap energy of TiO_2 is changed for different TiO_2 nanostructures.     

Calculations of physical properties of pure and doped crystals: Ab initio and semi-empirical methods in application to YAlO3:Ce and TiO2

In this paper we demonstrate that two independent methods of calculations (DFT based ab initio and semi-empirical crystal field theory) can be used to form a complementary picture of the optical and electronic properties of the doped host and impurity ion. The crystals considered in the present paper are: (i) YAlO₃:Ce³⁺ and (ii) two dominant phases of TiO₂—rutile and anatase. As an example, detailed calculations of the band structure and crystal field energy level scheme of YAlO₃:Ce³⁺ are reported. From the analysis of the band structure and density of states, the character of the YAlO₃ energetic bands and positions of the Ce impurity energy levels were established. It was also shown how the ab initio methods can be used for calculations of the structural properties of solids under elevated pressure. Taking the two dominant phases of TiO₂ as an example, it was demonstrated how the elastic properties can be extracted from the calculated unit cell’s volume at different pressures. Particular attention was paid to the microscopic effects of crystal field, which were evidenced by the pressure-induced changes of the structure and shape of distribution of the Ti 3d electrons density of states. It was demonstrated how the difference in crystal structure of the anatase and rutile phases leads to remarkable difference in microscopic crystal field effects, which was explained by different Ti-O distances in both phases. In addition, the pressure dependence of the band gaps for anatase and rutile was investigated. It was shown that the hydrostatic pressure leads to the band gap narrowing in anatase and band gap widening in rutile, with pressure coefficients +0.00681 eV/GPa for rutile and −0.0088 eV/GPa for anatase.     

掺Ge锐钛矿相TiO_2光学性质的计算

合理的掺杂是改善TiO_2活性,使其光催化性能在可见光照射下发挥作用的最有效途径之一,本文利用基于密度泛函理论的第一原理全电势线性缀加平面波方法计算掺Ge锐钛矿相TiO_2介电函数的实部、虚部和光学吸收系数.计算结果显示掺Ge锐钛矿相TiO_2介电函数虚部谱发生蓝移,与实验趋势相符;通过不用剪刀算符和固定晶格常数两方案研究掺Ge前后光谱的平移,得到蓝移是由于Ge原子替代Ti原子后晶胞体积减小造成.     

GW quasiparticle bandgaps of anatase TiO2 starting from DFT + U

We investigate the quasiparticle band structure of anatase TiO(2), a wide gap semiconductor widely employed in photovoltaics and photocatalysis. We obtain GW quasiparticle energies starting from density-functional theory (DFT) calculations including Hubbard U corrections. Using a simple iterative procedure we determine the value of the Hubbard parameter yielding a vanishing quasiparticle correction to the fundamental bandgap of anatase TiO(2). The bandgap (3.3 eV) calculated using this optimal Hubbard parameter is smaller than the value obtained by applying many-body perturbation theory to standard DFT eigenstates and eigenvalues (3.7 eV). We extend our analysis to the rutile polymorph of TiO(2) and reach similar conclusions. Our work highlights the role of the starting non-interacting Hamiltonian in the calculation of GW quasiparticle energies in TiO(2) and suggests an optimal Hubbard parameter for future calculations.