Ba_2SbGaS_5 : Solid-state Synthesis, Crystal and Electronic Structures, and Property Characterization

Single crystal of Ba2SbGaSs has been synthesized by the high temperature solidstate reaction method. The compound crystallizes in the orthorhombic space group Pnma with a = 12.177（4）, b = 8.880（3）, c = 8.982（3） A, V= 971.4（6） A3, Z = 4, De = 4.284 g/cm3,μ = 14.487 mm-1, F（000） - 1096, the final R = 0.0171 and wR = 0.0384 for all data. The structure comprises an infinite one-dimensional 1∞[SbGaS5]4- anionic chain constructed from the GaS4 tetrahedra and the SbS5 polyhedra via sharing edge alternately. The paralleled 1∞[SbGaS5]4anionic chains engage with each other and form the two-dimensional Sb-Ga-S layer perpendicular to a-axis with the isolated Ba2＋ cations arranged between layers. The IR spectrum and the UV-Vis spectrum have been investigated. Also, the first-principles band structure and density of states calculations indicate that the compound belongs to indirect semiconductor with the band gap of 2.1 eV, which is supported by the UV-Vis diffuse reflectance results.

First-Principles Studies the Lattice Constants and the Electronic Structures of Diluted Magnetic Semiconductors (In,Mn)As

Lattice constants and electronic structures of diluted magnetic semiconductors （ In, Mn ） As were investigated using the first principles LMTO-ASA band calculation by assuming supercell structures. Three concentrations of the 3 d impurities were studied （ x = 1/2, 1/4, 1/8）. The effect of varying Mn coucentrations on the lattice constants and the electronic structures are shown.

Role of buffer layer in electronic structures of iron phthalocyanine molecules on Au(111)

We investigate the electronic structures of one and two monolayer iron phthalocyanine （FePc） molecules on Au（111） surfaces. The first monolayer FePc is lying flat on the Au（111） substrate, and the second monolayer FePc is tilted at -15° relative to the substrate plane along the nearest neighbour [101] direction with a lobe downward to the central hole of the unit cell in the first layer. The structural information obtained by first-principles calculations is in agreement with the experiment results. Furthermore, it is demonstrated that the electronic structures of FePc molecules in one-monolayer FePc/Au（111） system are perturbed significantly, while the electronic structures of FePc molecules in the second monolayer in two-monolayer FePc/Au（111） system remain almost unchanged due to the screening of the buffer layer on Au（111）.

First-principles calculations of structural and electronic properties of Tl_xGa_(1-x)As alloys

The zincblende ternary alloys Tl_xGa_（1-x） As（0 〈 x 〈 1） are studied by numerical analysis based on the plane wave pseudopotential method within the density functional theory and the local density approximation. To model the alloys,16-atom supercells with the 2 × 2 × 2 dimensions are used and the dependency of the lattice parameter, bulk modulus,electronic structure, energy band gap, and optical bowing on the concentration x are analyzed. The results indicate that the ternary Tl_xGa_（1-x） As alloys have an average band gap bowing parameter of 4.48 eV for semiconductor alloys and 2.412 eV for semimetals. It is found that the band gap bowing strongly depends on composition and alloying a small Tl content with GaAs produces important modifications in the band structures of the alloys.

Electronic States of Difluorocarbene Calculated by Multireference Configuration Interaction Method

We investigate the geometries and energies of seven electronic states X-1A1, A1B1, a-3B1, B-1A2,b-3A2, C1B2 and c-3B2 of CF2 carbene using internally contracted multireference configuration interaction methods including Davidson correction （icMRCIq-Q） with different basis sets aug-cc-pVXZ （X=T, Q, 5）. For the first time, the potential energy curves of electronic states of CF2 related icMRCI＋Q/aug-cc-pVTZ level. The ab initio results will and dynamics of electronic states of CF2 radical. to the lowest dissociation limit are calculated at the further increase our understanding of the structures

First-Principles Calculation on Geometric,Electronic and Optical Properties of Fully Fluorinated Stanene:a Large-Gap Quantum Spin Hall Insulator

The searches for large-gap quantum spin Hall insulators are important for both practical and fundamental inter- ests. In this work, we present a theoretical observation of the two-dimensional fully fluorinated stanene （SnF） by means of density functional theory. Remarkably, a significant spin-orbit coupling is observed for the SnF monolayer in the valence band at the F point, with a considerable indirect band gap of 278 meV. The direct gap of the SnF monolayer is at the F point, which is slightly larger by as much as 381 meV. In addition, the elastic modulus of the SnF monolayer is about 20J/m^2, which is comparable with the in-plane stiffness of black phos- phorus monolayer along the x-direction （~28.94 J/m^2）. Finally, the optical properties of stanene, SnF monolayer and stanene/SnF bilayer are calculated, in which the stanene/SnF bilayer is supposed to be an attractive sunlight absorber.

QUANTUM CHEMICAL CALCULATIONS ON THE ELECTRONIC STRUCTURE AND SPECTRA OF[Mo_3O_4-nSn]^(4+)(n=O-4)CLUSTER CATIONS

The electronic structure and spectra of [Mo3O4-nSn]^(4+)(n=0-4) cations were calculated by means of INDO/CI quantum chemistry method to account for the experimental data of their spectra in water solutions.

Impact of Arsenic Related Defects on Electronic Performance of ZrO2/GaAs:Density Functional Theory Calculations

Arsenic can diffuse into high-κ dielectrics during OaAs-based metal oxide semiconductor transistor process, which causes the degradation of gate dielectrics. To explore the origins of the degradation, we employ nonlocal B3LYP hybrid functional to study arsenic related defects in ZrO2. Via band alignments between the OaAs and ZrO2, we are able to determine the defect formation energy in the GaAs relative to the ZrO2 band gap and assess how they will affect the device performance. Arsenic at the interstitial site serves as a source of positive fixed charge while at the oxygen or zirconium substitutional site changes its charge state within the band gap of GaAs. Moreover, it is found that arsenic related defects produce conduction band offset reduction and gap states, which will increase the gate leakage current.

Theoretical calculations of structural, electronic, and elastic properties of CdSe_(1-x)Te_x:A first principles study

The plane wave pseudo-potential method was used to investigate the structural, electronic, and elastic properties of Cd Se_（1-x）Te_x in the zinc blende phase. It is observed that the electronic properties are improved considerably by using LDA ＋ U as compared to the LDA approach. The calculated lattice constants and bulk moduli are also comparable to the experimental results. The cohesive energies for pure Cd Se and Cd Te binary and their mixed alloys are calculated. The second-order elastic constants are also calculated by the Lagrangian theory of elasticity. The elastic properties show that the studied material has a ductile nature.

Synthesis,Crystal Structure,and Optical Property of Zero-dimensional Quaternary Thioborate：Ba9B3GaS15

A new zero-dimensional（0D） thioborate Ba_9B_3GaS_（15） has been discovered by conventional high-temperature solid-state reaction. The compound crystallizes in orthorhombic space group Pbca with a = 8.4759（8）,b = 22.266（2）,c = 31.426（3） ？,V = 5931（2） ？~3,Z = 8,Mr = 1819.11,Dc = 4.075 g/cm3,μ = 13.684 mm^（-1）,F（000） = 6320,S = 1.034,（Δρ）max = 5.039,（Δρ）min = –5.409 e/？~3,the final R = 0.0362 and w R = 0.1053 for 19243 observed reflections with I 〉 2σ（I）. The structure is constructed by discrete [BS_3]^（3–） trigonal planes and isolated [GaS_4]^（5–） tetrahedra with Ba^（2＋） and isolated S^（2–） filled among them. The UV-Vis-near-IR spectrum reveals a wide band gap of 3.15 eV that agrees with the electronic structure calculation.

Surface for methane combustion:O(^3P)+CH4→OH+CH3

Kinetic investigations including quasi-classical trajectory and canonical unified statistical theory method calculations are carried out on a potential energy surface for the hydrogen-abstraction reaction from methane by atom O(^3P).The surface is constructed using a modified Shepard interpolation method.The ab initio calculations are performed at the CCSD(T)level.Taking account of the contribution of inner core electrons to electronic correlation interaction in ab initio electronic structure calculations,modified optimized aug-cc-pCVQZ basis sets are applied to the all-electrons calculations.On this potential energy surface,the triplet oxygen atom attacks methane in a near-collinear H-CH3 direction to form a saddle point with barrier height of 13.55 kcal/mol,which plays a key role in the kinetics of the title reaction.For the temperature range of 298-2500 K,our calculated thermal rate constants for the O(^3P)+CH4→OH+CH3 reaction show good agreement with relevant experimental data.This work provides detailed mechanism of this gas-phase reaction and a theoretical guidance for methane combustion.

Electron-correlation-induced band renormalization and Mott transition in Ca_(1-x)Sr_xVO_3

We present the local density approximate＋Gutzwiller results for the electronic structure of Cal-xSrxVOa. The substitution of Sr2＋ by Ca2＋ reduces the bandwidth, as the V-O-V bond angle decreases from 180° for SrVO3 to about 160° for CaVO3. However, we find that the bandwidth decrease induced by the V-O-V bond angle decrease is smaller as compared to that induced by electron correlation. In correlated electron systems, such as Cal-=Sr=VOa, the correlation effect of 3d electrons plays a leading role in determining the bandwidth. The electron correlation effect and crystal field splitting collaboratively determine whether the compounds will be in a metal state or in a Mort-insulator phase.

Defect-induced ferromagnetism in rutile TiO_2 : A first-principles study

Based on first-principles calculations, the electronic and magnetic properties of undoped and Li-doped rutile TiO2 have been studied. The results demonstrate that a cation vacancy can arouse ferromagnetism in TiO2 and the magnetic moment mainly comes from p orbitals of O atoms around the Ti vacancy. However, the Ti vacancy under normal conditions is very difficult to form due to its high formation energy. Our calculations indicate that Li-doped TiO2 can reduce the formation energy while keeping the magnetism. The large magnetization energy indicates that Li-doped TiO2 is a promising room-temperature diluted magnetic semiconductor.

THE CALCULATION OF RATE CONSTANT OF ELECTRON TRANSFER REACTION AT ELECTRODES

After the electron transfers from the metal electrode to the Fe3+(H2O)(6) ion, the free energy of activation of this electron transfer reaction is calculated, then using the transition probability which is calculated by the perturbed degeneration theory and the Fermi golden rule,, the rate constant is gotten. Compared with the experimental results, it is satisfactory.

Modified Atomic Orbital Theory of the O+ Ion Originating from 2D0 and 4S0 Metastable States

We report in this paper energy positions of the 2D0_2s22p2(1D)nd(2F);2D0_2s22p2(1D)nd(2D);2D0_2s22p2(1D)nd(2P);2D0_2s22p2(1D)ns(2D);2D0_2s22p3(3D)np(2P);2D0_2s22p3(3D0)np(2F), and 4S0_2s22p3(5S0)np(4P) Rydberg series in the photoionization spectra originating from 2D0 and 4S0 metastable states of O+ ion. Calculations are performed up to n = 20 using the Modified Orbital Atomic Theory (MAOT) [1]. The present results are compared to the experimental data of Aguilar et al. [2] which are the only available values. The accurate data presented in this work may be a useful guideline for future experimental and other theoretical studies.

Photoionization Study of the 2<i>s²2p²(¹D)ns(²D), 2s²2p²(¹D)nd(²P), 2s²2p²(¹D)nd(²S), 2s²2p²(¹S)nd²D</i>, and <i>2s²2p³(³P)np(²D)</i>Rydberg Series of O+ Ions via the Modified Atomic Orbital Theory

We report in this paper energy positions of the 2P°_2s22p2(1D)nd 2P, 2P°_2s22p2(1D)nd 2S, 2P°_2s22p2(1D)ns 2D, 2P°_2s22p2(1S)nd 2D, and 2P°_2s22p3(3P)np 2D Rydberg series in the photoionization spectra originating from 2P° metastable state of O+ ions. Calculations are performed up to n = 30 using the Modified Orbital Atomic Theory (MAOT). The present results are compared to the experimental data of Aguilar which are the only available values. The accurate data presented in this work may be a useful guideline for future experimental and other theoretical studies.

Relativistic Reduction of the Electron-Nucleus Force in Bohr’s Hydrogen Atom and the Time of Electron Transition between the Neighbouring Quantum Energy Levels

The aim of the paper is to get an insight into the time interval of electron emission done between two neighbouring energy levels of the hydrogen atom. To this purpose, in the first step, the formulae of the special relativity are applied to demonstrate the conditions which can annihilate the electrostatic force acting between the nucleus and electron in the atom. This result is obtained when a suitable electron speed entering the Lorentz transformation is combined with the strength of the magnetic field acting normally to the electron orbit in the atom. In the next step, the Maxwell equation characterizing the electromotive force is applied to calculate the time interval connected with the change of the magnetic field necessary to produce the force. It is shown that the time interval obtained from the Maxwell equation, multiplied by the energy change of two neighbouring energy levels considered in the atom, does satisfy the Joule-Lenz formula associated with the quantum electron energy emission rate between the levels.

First principles study of structural, electronic, elastic and magnetic properties of cerium and praseodymium hydrogen system REH_x(RE:Ce, Pr and x=2, 3)

The structural, electronic, elastic and magnetic properties of cerium, praseodymium and their hydrides REH x（RE=Ce, Pr and x=2, 3） were investigated by the first principles calculations based on density functional theory using the Vienna ab-initio simulation package. At zero pressure all the hydrides were stable in the ferromagnetic state. The calculated lattice parameters were in good agreement with the experimental results. The bulk modulus decreased with the increase in the hydrogen content for these hydrides. The electronic structure revealed that di-hydrides were metallic whereas trihydrides were half metallic at zero pressure. A pressure-induced structural phase transition from cubic to hexagonal phase was predicted in these hydrides. The computed elastic constants indicated that these hydrides were mechanically stable at zero pressure. The calculated Debye temperature values were in good agreement with experimental and other theoretical results. A half metallic to metallic transition was also observed in REH3 under high pressure. Ferromagnetism was quenched in these hydrides at high pressures.

Parallel Mesh Refinement of Higher Order Finite Elements for Electronic Structure Calculations

The finite element method is a promising method for electronic structure calculations.In this paper,a new parallelmesh refinementmethod for electronic structure calculations is presented.Some properties of the method are investigated to make itmore efficient andmore convenient for implementation.Several practical issues such as distributed memory parallel computation,less tetrahedra prototypes,and the assignment of the mesh elements carried out independently in each sub-domain will be discussed.The numerical experiments on the periodic system,cluster and nano-tube are presented to demonstrate the effectiveness of the proposed method.

Investigation of Structural, Electronic and Mechanical Properties of Rubidium Metal Hydrides RbMH_4(M=B, Al, Ga)

Ab initio calculations are performed to investigate the structural stability, electronic structure and mechanical properties of rubidium metal hydrides RbMH4（M = B, Al, Ga） for five different crystal structures, namely hexagonal（P63mc）, tetragonal（P42/nmc）, tetragonal（P421c）, orthorhombic（Pnma） and monoclinic（P21/c）. Among the considered structures, tetragonal（P421c） phase is found to be the most stable one for these metal hydrides at normal pressure. A pressure-induced structural phase transition from tetragonal（P421c） to monoclinic（P21/c） phase is observed in all the three metal hydrides. The electronic structure reveals that these hydrides are wide band gap semiconductors. The calculated elastic constants indicate that these alkali metal tetrahydrides are mechanically stable at normal pressure.