Electronic structure and optical properties of In-doped SrTiO3 by density function theory

The effect of In doping on the electronic structure and optical properties of SrTiO3 is investigated by the first-principles calculation of plane wave ultra-soft pseudo-potential based on the density function theory （DFT）. The calculated results reveal that due to the hole doping, the Fermi level shifts into valence bands （VBs） for SrTi1-x InxO3 with x = 0.125 and the system exhibits p-type degenerate semiconductor features. It is suggested according to the density of states （DOS） of SrTi0.875In0.125O3 that the band structure of p-type SrTIO3 can be described by a rigid band model. At the same time, the DOS shifts towards high energies and the optical band gap is broadened. 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 film. The optical transmittance of In doped SrTiO3 is higher than 85% in a visible region, and the transmittance improves greatly. And the cut-off wavelength shifts into a blue-light region with the increase of In doping concentration.

Electronic structure and flotability of gold-bearing pyrite:A density functional theory study

Various incorporation of Au in pyrite and its effects on the geometrical structure,electronic structure and flotability of pyrite were theoretically investigated and fully discussed by performing density functional theory(DFT).The calculated incorporation energy shows that gold would most likely exist in pyrite via incorporating into interstitial lattice sites in the absence of As impurity.As a result of incorporated Au,the covalence levels of the S—Fe and S—S bonds are changed,and the tonicity of Au—S bonds and antibonding of Au—Fe bonds are found to form in the pyrite,which would change the natural flotability of pyrite.The Au impurity energy levels are introduced into the energy band and result in the transformation of pyrite semiconductivity type.The calculated band-gap value suggests that the incorporated Au significantly decreases pyrite semiconductivity level,which enhances the formation and the adsorption stability of dixanthogen during pyrite flotation.The DOS results reveal that the stability and depression difficulty level of pyrites increases in the following order:Fe_(32)S_(63)As<Fe_(32)S_(64)<Fe_(32)S_(63)As Au<Fe_(32)S_(64)Au.

Crystal Structure and Density Functional Theory Studies of (p-Methoxyphenyl) Thiosemicarbazide

The title compound [CH3OC6H4NHNHCSNH2] has been characterized by ele- mental analysis, IR, electronic absorption spectra and X-ray single-crystal diffraction. It crystallizes in the monoclinic system, space group C2/c with a = 25.071(5), b = 5.9292(12), c = 14.938(3) ?, β = 118.40(3)o, Mr = 197.26 (C8H11N3OS), V = 1953.3(7) ?3, Z = 8, Dc = 1.342 g/cm3, F(000) = 832, μ = 0.296 mm-1, R = 0.0647 and wR = 0.1433. In the crystal lattice, there exist some intermolecular hydrogen bonds, π-π stacking interactions and C–H…π supramolecular interactions to stabilize the crystal structure. The density functional theory (DFT) calculations at the B3LYP/6-31G* level, charge distributions and thermodynamic properties at different temperature have been performed, showing the sulfur and nitrogen atoms have bigger negative charges because they are the potential sites reacting with the metallic ions.

Electronic structures and magnetoelectric properties of tetragonal BaFeO_3:an ab initio density functional theory study

First-principles calculations have been performed to investigate the ground state electronic properties of BaFeO3 （BFO）. Local spin density approximation （LSDA） plus U （LSDA＋U） treatment modified the metallic behaviour to insulated one with a band gap of 4.12eV. The spontaneous polarization was found to be 89.3μC/cm^2 with Berry phase scheme in terms of the modern theory of polarization. Fe-3d eg were split into two singlet states （dz2 and dx2-v2）, and Fe-3d t2g were split into one doublet states（dze and dyz） and one singlet states（dzy） after Fe and O displaced along the c axis. Meanwhile the occupation numbers of dx2, dxz, dyz and OT pz （on the top of Fe） were increased at the expense of those in xy plane. Our results showed that it was the sensitivity of hybridization to ferroelectric distortions, not just the total change of hybridization, that produced the possibility of ferroelectricity. Moreover, the increasing occupation numbers of OT pz and Fe dz2 favoured the 180° coupling between Fe-3d eg and Fe-3d t2g, leading to ferromagnetic ordering, which has been confirmed by the increase of magnetic moment by 0.13μB per formula unit in the polarized direction. Hence, the magnetization can be altered by the reversal of external electric field.

Electronic structure and optical properties of Nb-doped Sr_2TiO_4 by density function theory calculation

This paper investigates the effect of Nb doping on the electronic structure and optical properties of Sr2TiO4 by the first-principles calculation of plane wave ultra-soft pseudo-potential based on density functional theory （DFT）.The calculated results reveal that due to the electron doping,the Fermi level shifts into conduction bands（CBs） for Sr2NbxTi1-xO4 with x=0.125 and the system shows n-type degenerate semiconductor features. Sr2TiO4 exhibits optical anisotropy in its main crystal axes,and the c-axis shows the most suitable crystal growth direction for obtaining a wide transparent region.The optical transmittance is higher than 90% in the visible range for Sr2Nb0.125Ti0.875O4.

Geometries, Electronic Structures, and Electron Detachment Energies of Small Boron Sulfide Anions: A Density Functional Theory Investigation

A density functional theory investigation on the geometries, electronic structures, and electron detachment energies of BS, BS2, B（BS）2 and B（BS）3 has been performed in this work. The linear ground-state structures of BS （C∞v, ^1∑^＋） and BS2^- （O∞h, ^1∑g^＋） prove to be similar to the previously reported BO and BO2 with systematically lower electron detachment energies. Small boron sulfide clusters are found to favor the formation of -B=S groups which function basically as a-radicals and dominate the ground-state structures of the systems. The perfect linear B（BS）2^-（D∞h, ^3∑g） and beautiful equilateral triangle B（BS）3^- （D3h,^2A1”） turn out to be analogous to the well-known C2v BH2 and O3h BH3, respectively. The electron affinities of BS, BS2, B（BS）2 and B（BS）3 are predicted to be 2.3, 3.69, 3.00 and 3.45 eV, respectively. The electron detachment energies calculated for BS^-, BS2^-, B（BS）2^-, and B（BS）3^- may facilitate future photoelectron spectroscopy measurements to characterize the geometrical and electronic structures of these anions.

Orbital-Free Density Functional Theory for Molecular Structure Calculations

We give here an overview of the orbital-flee density functional theory that is used for modeling atoms and molecules. We review typical approximations to the kinetic energy, exchange-correlation corrections to the kinetic and Hartree energies, and constructions of the pseudopotentials. We discuss numerical discretizations for the orbital-free methods and include several numerical results for illustrations.

Structures and electronic properties of Si_m N_(8-m)(0

The geometries, electronic structures and related properties of SimN8-m（0 〈 m 〈 8） clusters are studied using density functional theory （DFT） with hybrid functional B3LYP. The calculated results reveal several trends. For any stoichiometric clusters, the lowest energy isomers with an alteration of N and Si atoms are favourable in energy if the numbers of Si and N atoms are large enough to form ... Si N-Si-N... alternative chains. The bond lengths of single Si-N bonds are very close to the corresponding values of the bulk and other SiN clusters. The geometries for N-rich and Si4N4 clusters are planar structures, but three-dimensional structures are favourable in energy for Si-rich clusters. With the increase of m, the isotropic polarizability and average polarizability increase, the total binding energies generally decrease, the HOMO-LUMO gap and vertical ionization potential oscillate with increasing number of valence electrons, and their values with even valence electrons are larger than those with odd valence electrons. The atomic charges, IR and Raman properties are also reported.

Comparison of Fungicidal Difference of Two Arylpyrazoles Based on the Crystal Structures, Density Functional Theory Calculation and Molecular Docking

Two arylpyrazoles I andⅡwere synthesized and characterized by NMR and single-crystal X-ray diffraction.Compound I displayed 71.4%fungicidal inhibition rate against Rhizoctonia solani at 0.1 ppm,better than the control pyraclostrobin,whereasⅡhad little activity.Their fungicidal difference was discussed from theoretic level based on the crystal structure,density functional theory(DFT)calculation and molecular docking.The B3 LYP/6-31G^**level was employed to explore the HOMO-LUMO energy gap and charge distribution.Molecular docking was performed on the probable target protein bc1-enzyme complex.DFT calculation and docking studies supported the in vitro findings.

Preparation,Crystal Structure and Density Functional Theory Calculations of the Ion-pair Compound [Cl2Bz(3-MeQl)](TCNQ)

A novel compound [Cl2Bz（3-MeQl） ]（TCNQ） （[Cl2Bz（3-MeQl） ]^＋ = 1-（3,4-dichlo-robenzyl） 3-methlquinoline cation,TCNQ-= 7,7,8,8-tetracyanoquinodimethanide anion） has been synthesized by the reaction of [Cl2Bz（3-MeQl） ]Br and LiTCNQ,and its structure was determined by single-crystal X-ray diffraction. The crystal belongs to monoclinic,space group P21/c. The structure analysis shows that the anions are stacked into a column with isolated π-dimers,and there is one type of TCNQ entries（TCNQ^-） ,in agreement with the IR spectra analysis and density functional theory calculations of the compound. The most prominent structural features are the completely segregated stacking columns of the TCNQ- anions and [Cl2Bz（3-MeQl）]＋ cations.

Derivation and Creation of Confucian Cultural Structure and Function Theory from the Theory of Material Structure and Function

By studying the relationship between physical structure and function in physical chemistry, the author breaks through the limitation of the western narrow social and cultural structure and function theory, and further derives and founds the Confucian cultural structure and function theory, thus creating a new research methodology and broadening the research horizon. Through the research, it is found that the Confucian culture structure consists of the hard structure ＂ritual＂ and the soft structure ＂benevolence＂, and based on this constructs three-outline, five- principal, four-moral, eight- virtul, five cardinal principals and other Confucian culture, so that these have a social management function, resulting in a 2000-year stable Chinese social order, which also provides reference for the social management of Chinese government today.

Density-functional theory investigation of electronic structure,elastic properties,optical properties,and lattice dynamics of Ba_2Zn WO_6

The electronic structures, optical dielectric functions, elastic properties, and lattice dynamics of Ba2ZnWO6 have been investigated by using the generalized gradient approximation. The density of states and distributions of charge density show that O and Ba tend toward ionic bond, but O and W or Zn display the covalent bond character. The calculated energy band structure shows that Ba2ZnWO6 is a wide indirect band gap semiconductor. The static value 2.28 of the refractive index is attained. The analysis of the elastic properties of Ba2ZnWO6 indicates a rather weak elastic anisotropy. The phonon dispersion is calculated, suggesting no structural instability, which is agreement with the recent low temperature neutron diffraction experiments. The mensurability Cv （phonon heat capacity） as the function of the temperature is also calculated to judge our results for future experiment.

A density-functional theory for (BAs) n clusters (n=1-14):structures,stabilities and electronic properties

This paper investigates the lowest-energy structures, stabilities and electronic properties of （BAs）n clusters （n=1- 14） by means of the density-functional theory. The results show that the lowest-energy structures undergo a structural change from two-dimensional to three-dimensional when n ： 4. With the increase of the cluster size （n=6）, the （BAs）n clusters tend to adopt cage-like structures, which can be considered as being built from B2As2 and six-membered rings with B-As bond alternative arrangement. The binding energy per atom, second-order energy differences, vertical electron affinity and vertical ionization potential are calculated and discussed. The caculated HOMO-LUMO gaps reveal that the clusters have typical semiconductor characteristics. The analysis of partial density of states suggests that there are strong covalence and molecular characteristics in the clusters.

Structures, stabilities, and electronic properties of F-doped Sin （n=1～12） clusters：Density functional theory investigation

The geometries, stabilities, and electronic properties of FSin （n=1～12） clusters are systematically investigated by using first-principles calculations based on the hybrid density-functional theory at the B3LYP/6-311G level. The geometries are found to undergo a structural change from two-dimensional to three-dimensional structure when the cluster size n equals 3. On the basis of the obtained lowest-energy geometries, the size dependencies of cluster properties, such as averaged binding energy, fragmentation energy, second-order energy difference, HOMO–LUMO （highest occupied molecular orbital–lowest unoccupied molecular orbital） gap and chemical hardness, are discussed. In addition, natural population analysis indicates that the F atom in the most stable FSin cluster is recorded as being negative and the charges always transfer from Si atoms to the F atom in the FSin clusters.

Hydroelastic Analysis of Very Large Floating Structures Using Plate Green Functions

Great attention has been paid to the development of very large floating structures. Owing to their extreme large size and great flexibility, the coupling between the structural deformation and fluid motion is significant. This is a typical problem of hydroelasticity. Efficient and accurate estimation of the hydroelastic response of very large floating structures in waves is very important for design. In this paper, the plate Green function and fluid Green function are combined to analyze the hydroelastic response of very large floating structures. The plate Green function here is a new one proposed by the authors and it satisfies all boundary conditions for free-free rectangular plates on elastic foundations. The results are compared with some experimental data. It is shown that the method proposed in this paper is efficient and accurate. Finally, various factors affecting the hydroelastic response of very large floating structures are also studied.

Structural and functional connectivity of the whole brain and subnetworks in individuals with mild traumatic brain injury:predictors of patient prognosis

Patients with mild traumatic brain injury have a diverse clinical presentation,and the underlying pathophysiology remains poorly understood.Magnetic resonance imaging is a non-invasive technique that has been widely utilized to investigate neuro biological markers after mild traumatic brain injury.This approach has emerged as a promising tool for investigating the pathogenesis of mild traumatic brain injury.G raph theory is a quantitative method of analyzing complex networks that has been widely used to study changes in brain structure and function.However,most previous mild traumatic brain injury studies using graph theory have focused on specific populations,with limited exploration of simultaneous abnormalities in structural and functional connectivity.Given that mild traumatic brain injury is the most common type of traumatic brain injury encounte red in clinical practice,further investigation of the patient characteristics and evolution of structural and functional connectivity is critical.In the present study,we explored whether abnormal structural and functional connectivity in the acute phase could serve as indicators of longitudinal changes in imaging data and cognitive function in patients with mild traumatic brain injury.In this longitudinal study,we enrolled 46 patients with mild traumatic brain injury who were assessed within 2 wee ks of injury,as well as 36 healthy controls.Resting-state functional magnetic resonance imaging and diffusion-weighted imaging data were acquired for graph theoretical network analysis.In the acute phase,patients with mild traumatic brain injury demonstrated reduced structural connectivity in the dorsal attention network.More than 3 months of followup data revealed signs of recovery in structural and functional connectivity,as well as cognitive function,in 22 out of the 46 patients.Furthermore,better cognitive function was associated with more efficient networks.Finally,our data indicated that small-worldness in the acute stage could serve as a predictor of longitudinal changes in connectivity in patients with mild traumatic brain injury.These findings highlight the importance of integrating structural and functional connectivity in unde rstanding the occurrence and evolution of mild traumatic brain injury.Additionally,exploratory analysis based on subnetworks could serve a predictive function in the prognosis of patients with mild traumatic brain injury.

Structure,electronic,and nonlinear optical properties of superalkaline M_(3)O(M=Li,Na)doped cyclo[18]carbon

Cyclo[18]carbon has received considerable attention thanks to its novel geometric configuration and special electronic structure.Superalkalis have low ionization energy.Doping a superalkali in cyclo[18]carbon is an effective method to improve the optical properties of the system because considerable electron transfer occurs.In this paper,the geometry,bonding properties,electronic structure,absorption spectrum,and nonlinear optical(NLO)properties of superalkaline M_(3)O(M=Li,Na)-doped cyclo[18]carbon were studied by using density functional theory.M_(3)O and the C_(18) rings are not coplanar.The C_(18) ring still exhibits alternating long and short bonds.The charge transfer between M_(3)O and C_(18) forms stable[M_(3)O]+[C_(18)]-ionic complexes.C_(18)M_(3)O(M=Li,Na)shows striking optical nonlinearity,i.e.,their first-and second-order hyperpolarizability(βvec andγ||)increase considerably atλ=1907 nm and 1460 nm.

Tailoring local structures of atomically dispersed copper sites for highly selective CO_(2) electroreduction

Atomically‐dispersed copper sites coordinated with nitrogen‐doped carbon(Cu–N–C)can provide novel possibilities to enable highly selective and active electrochemical CO_(2) reduction reactions.However,the construction of optimal local electronic structures for nitrogen‐coordinated Cu sites(Cu–N_(4))on carbon remains challenging.Here,we synthesized the Cu–N–C catalysts with atomically‐dispersed edge‐hosted Cu–N_(4) sites(Cu–N_(4)C_(8))located in a micropore between two graphitic sheets via a facile method to control the concentration of metal precursor.Edge‐hosted Cu–N_(4)C_(8) catalysts outperformed the previously reported M–N–C catalysts for CO_(2)‐to‐CO conversion,achieving a maximum CO Faradaic efficiency(FECO)of 96%,a CO current density of–8.97 mA cm^(–2) at–0.8 V versus reversible hydrogen electrode(RHE),and over FECO of 90%from–0.6 to–1.0 V versus RHE.Computational studies revealed that the micropore of the graphitic layer in edge‐hosted Cu–N_(4)C_(8) sites causes the d‐orbital energy level of the Cu atom to shift upward,which in return decreases the occupancy of antibonding states in the*COOH binding.This research suggests new insights into tailoring the locally coordinated structure of the electrocatalyst at the atomic scale to achieve highly selective electrocatalytic reactions.

Studies of Structural and Thermodynamic Properties for Polychlorinated Thianthrenes by Density Functional Theory

The structural and thermodynamic （PCTAs） in the ideal gas state at 298.15 K and 1.013 properties of 75 polychlorinated thianthrenes ×10^5 Pa have been calculated at the B3LYP/6- 31G＊ level using Gaussian 98 program. Based on the output data of Gaussian, the isodesmic reactions were designed to calculate standard enthalpy of formation （△fH^θ） and standard free energy of formation （△fH^θ） of PCTAs congeners. The relations of these thermodynamic parameters with the number and position of C1 atom substitution （Npcs） were discussed, and it was found that there exists high correlation between thermodynamic parameters （total energy （TE）, zero-point vibrational energy （ZPE）, thermal correction to energy （Eth）, heat capacity at constant volume （Cv^θ）, entropy （S^θ）, enthalpy （H^θ）, free energy （G^θ）, standard enthalpies of formation （△fH^θ） and standard Gibbs energies of formation （△fG^θ）） and Npcs. On the basis of the relative magnitude of their △fG^θ, the order of relative stability of PCTA congeners was theoretically proposed. In addition, the correlations between structural parameters and Npcs were also discussed. The good correlations were found between molecular average polarizability （α）, energy of the highest occupied molecular orbital （EHOMO）, molecular volume （Vm） and Npcs, and all R^2 values are larger than 0.95. Moreover, it was supposed that the isomer groups with higher toxicity should be Tri-CTA and TCTA.