LaNi4.5Mn0.5储氢合金及氢化物的电子结构

基于密度泛函理论,采用总能量计算方法与结合超软赝势平面波函数方法,对LaNi4.5Mn0.5储氢合金及其氢化物的晶体几何结构进行了优化,计算了其相应的总体能量、晶体结构、能带结构、及态密度分布等,从理论上给出了其结构参数及性质.结果表明,锰取代3g位后合金晶胞略有膨胀,并伴随着晶体稳定性变差.LaNi4.5Mn0.5合金中EF附近的态密度贡献最主要来自La的p电子,以及Ni和Mn原子的d电子.     

Structural and electronic properties of fluorographene

The structural and electronic characteristics of fluorinated graphene are investigated based on first-principles density-functional calculations. A detailed analysis of the energy order for stoichiometric fluorographene membranes indicates that there exists prominent chair and stirrup conformations, which correlate with the experimentally observed in-plane lattice expansion contrary to a contraction in graphane. The optical response of fluorographene is investigated using the GW-Bethe-Salpeter equation approach. The results are in good conformity with the experimentally observed optical gap and reveal predominant charge-transfer excitations arising from strong electron-hole interactions. The appearance of bounded excitons in the ultraviolet region can result in an excitonic Bose-Einstein condensate in fluorographene.     

Compton profiles of MoP and WP: Validation of second order generalized gradient approximation

Recently, Zhao and Truhlar (J. Chem. Phys. 128, 184109, 2008) have constructed second order generalized gradient approximation (SOGGA) within the density functional theory. The authors have successfully tested the performance of SOGGA by computing lattice constants, cohesive energies, bond distances and few energetic quantities of different solids and molecules. In this paper, to establish the usefulness of SOGGA in deducing the momentum densities, we have compared our experimental Compton profiles of MoP and WP with those computed using GGA and SOGGA within density functional theory. It is seen that SOGGAPBE based Compton profiles of both the samples are in better agreement with the corresponding experimental data than those derived from BPBE-GGA. In addition, energy bands, density of states and relative nature of bonding in both the phosphides is explained in terms of equal-valence-electron-density profiles and Mulliken’s population analysis.     

Structural and electronic properties of C and BN nanotubes based on periodic fullerenes: A density functional theory study

The structural and electronic properties of C and BN nanotubes based on periodic fullerenes were studied using density functional theory. It was shown that these tubular structures are stable. The electronic band structures and density of states indicated that the C nanotubes based on periodic fullerenes are metals. The energy band gap was appeared by substitution of C atoms with B and N atoms. The BN nanotubes based on periodic fullerenes show semiconducting properties. Our results suggest that the nanotubes based on periodic fullerenes can be used to design of nanoelectronic devices.     

La2Ni7和LaMgNi7储氢合金电子结构的研究

采用密度泛函理论研究了La2Ni7和LaMg-Ni7储氢合金的电子结构,探讨了微观结构和合金宏观性能之间的关联性.结果表明,含Mg元素的LaMgNi7体系形成成键作用的Ni-Mg键,体系稳定性高于纯La2Ni7体系.同时LaMgNi7体系中的Ni-Ni键强度弱于La2Ni7体系中的相应键,降低了H进入体系的能量壁垒,改...     

Si掺杂锐钛矿相TiO2的电子能带结构

利用基于密度泛函理论的第一性原理方法对Si掺杂前、后锐钛矿相TiO2的电子能带结构、电子态密度以及吸收光谱进行计算。结果表明,Si掺杂导致锐钛矿相TiO2的禁带宽度略增大0.048 eV;掺杂前锐钛矿相TiO2的价带和导带主要由O的2p和Ti的3d轨道构成,Si掺杂后其价带和导带主要由Si的3p、Ti的4s和Ti的3d轨道构成;Si掺杂可导致锐钛矿相TiO2的吸收边蓝移。     

补偿型共掺杂ZnS电子特性的第一性原理计算

基于密度泛函理论的第一性原理平面波赝势方法,对ZnS(Cu,Cl、Br、I)共掺杂体系的晶格结构和电子性质进行了研究。结果表明,相对于单掺杂ZnS体系,补偿型的共掺ZnS体系形成能更低,更有利于提高可见光的催化效率,且由于p-d电子排斥效应使价带向高能方向展宽,而Cu的3p态与非金属原子的杂质态使导带底下移,从而使共掺杂ZnS体系的能带带隙变窄,尤其是CuZnBrS-ZnS带隙值减少了30%,从而延伸吸收边界到可见光区域。且CuZnBrS-ZnS中m*e/m*h相对较大,降低了电子-空穴对重组率,提高了量子效率。最后对补偿型共掺ZnS电子结构进行了讨论。     

Specific features of the electronic structure and optical properties of KPb2Br5: DFT calculations and X-ray spectroscopy measurements

Density functional theory (DFT) calculations are made in order to explore the total and partial densities of states of potassium dilead pentabromide, KPb₂Br₅, by using the augmented plane wave + local orbitals (APW + lo) method as incorporated in the WIEN2k package. The present calculations reveal that the principle contributors to the valence band of KPb₂Br₅ are the Pb 6s and Br 4p states contributing predominantly at the bottom and at the top of the band, respectively, while the bottom of the conduction band is formed mainly from contributions of the unoccupied Pb 6p states. The curves of total density of states derived by the present DFT calculations of KPb₂Br₅ are found to be in agreement with the experimental X-ray photoelectron valence-band spectrum of the compound studied. Comparison on a common energy scale of the X-ray emission bands representing the energy distribution of the valence Br p and K s states and the X-ray photoelectron valence-band spectrum of the KPb₂Br₅ single crystal indicate that the Br 4p and K 4s states contribute mainly at the top and in the upper portion of the valence band, respectively, being in agreement with data of the present DFT band-structure calculations of this compound. Principal optical characteristics of KPb₂Br₅, namely dispersion of the absorption coefficient, real and imaginary parts of dielectric function, electron energy-loss spectrum, refractive index, extinction coefficient and optical reflectivity are also studied by the DFT calculations.     

Electronic Structure Control of Tungsten Oxide Activated by Ni for Ultrahigh‐Performance Supercapacitors

Tuning the electron structure is of vital importance for designing high active electrode materials. Here, for boosting the capacitive performance of tungsten oxide, an atomic scale engineering approach to optimize the electronic structure of tungsten oxide by Ni doping is reported. Density functional theory calculations disclose that through Ni doping, the density of state at Fermi level for tungsten oxide can be enhanced, thus promoting its electron transfer. When used as electrode of supercapacitors, the obtained Ni‐doped tungsten oxide with 4.21 at% Ni exhibits an ultrahigh mass‐specific capacitance of 557 F g^?1 at the current density of 1 A g^?1 and preferable durability in a long‐term cycle test. To the best of knowledge, this is the highest supercapacitor performance reported so far in tungsten oxide and its composites. The present strategy demonstrates the validity of the electronic structure control in tungsten oxide via introducing Ni atoms for pseudocapacitors, which can be extended to other related fields as well.     

PbSe(001)表面特性的第一性原理研究

用第一性原理的密度泛函理论计算了PbSe（001）表面的几何结构和电子特性。计算结果表明：PbSe（001）表面几层原子出现明显的振荡弛豫现象,但没发生重构,第一、二原子间距减小,第二、三层原子间距增大,同时也发现表面层原子出现褶皱。该表面的直接带隙出现在X点,在导带底和价带顶附近出现4个表面共振态,另外两个表面态分别出现在-4．0eV附近和-11．5eV附近。     

Influence of substitutional doping on the electronic properties of carbon nanotubes with Stone Wales defects: density functional calculations

Abstract

In this work, we implemented density function theory to investigate the structural and the electronic properties of nitrogen doped single walled carbon nanotube under different orientations of Stone Wales defect. We have found that, the doped defected structures are more stable than the non-doped defected structures. Furthermore, doping defected carbon nanotubes with a nitrogen atom has significantly narrowed the band gap and slightly shifted the Fermi level toward the conduction band. Moreover, nitrogen substitution creates new band levels just above the Fermi level which exemplifies an n-type doping. However, the induced band gap is indirect band gap compared to direct band gap as in pristine carbon nanotubes. Furthermore, the electronic and structural properties of nitrogen doped carbon nanotube with Stone Wales defects is crucially affected by the dopant site as well as the orientations of Stone Wales defects.     

Electronic structure of YBa2Cu3O7 and YBa2Cu3O6—charge-self-consistent band structure calculations

Charge self-consistent LCAO band structure (CSCBS) calculations are reported for orthorhombic YBa₂Cu₃O₇ and tetragonal YBa₂Cu₃O₆ assuming ordered vacancy models. The effective atomic charges are used to study the charge transfer. In YBa₂Cu(1)₁Cu(2)₂O₇, the two types of copper atoms have their energy bands almost overlapping with effective valency of each copper as 7/3 (or effective valency of each oxygen as approximately — 13/7), so that electron hopping can take place without any loss or gain of energy while in YBa₂Cu(1)₁Cu(2)₂O₆, Cu(1)₁ is monovalent and Cu(2)₂ are divalent with significant difference in their bands. Therefore, YBa₂Cu₃O₇ should conduct much better compared to YBa₂Cu₃O₆. This corroborates the experimental observations that YBa₂Cu₃O₇ is a (super)conductor while YBa₂Cu₃O₆ is not. The calculated effective charges and DOS support the above view.     

Structure and properties of functional oxide thin films: insights from electronic-structure calculations

The confluence of state-of-the-art electronic-structure computations and modern synthetic materials growth techniques is proving indispensable in the search for and discovery of new functionalities in oxide thin films and heterostructures. Here, we review the recent contributions of electronic-structure calculations to predicting, understanding, and discovering new materials physics in thin-film perovskite oxides. We show that such calculations can accurately predict both structure and properties in advance of film synthesis, thereby guiding the search for materials combinations with specific targeted functionalities. In addition, because they can isolate and decouple the effects of various parameters which unavoidably occur simultaneously in an experiment-such as epitaxial strain, interfacial chemistry and defect profiles-they are able to provide new fundamental knowledge about the underlying physics. We conclude by outlining the limitations of current computational techniques, as well as some important open questions that we hope will motivate further methodological developments in the field.     

电子强关联对LaMnO_3电子结构的影响

本文利用密度泛函对LaMnO3的电子结构进行了计算。结果表明,LaMnO3反铁磁绝缘基态的形成主要依赖于Jahn-Teller畸变而不是电子强关联,但电子强关联效应对LaMnO3电子结构的影响巨大。为了获得正确的结果,本文计算时考虑了适当的电子强关联修正。通过分析比较,表明在位的库仑能U取3.5eV是一个合理的选择。     

四面体掺杂尖晶石结构Co1-xRexCr2O4(Re=Li、Na、K、Rb)的电子结构和光学性质

采用基于密度泛函理论(DFT)的平面波超软赝势方法, 计算了CoCr₂O₄及Li、Na、K和Rb四面体掺杂CoCr₂O₄的基态结构、电子结构和光学性质。计算结果表明: 一价离子四面体掺杂都导致晶格有微小的畸变, 使体系的稳定性降低, Rb掺杂的体系最稳定; 电子态密度的计算结果表明: 掺杂体系的导带主要有Co-3d和Cr-3d轨道电子构成, 掺杂离子改变了CoCr₂O₄导带的电子结构, 主要引起了导带Co-3d态密度峰的下移, 随着掺杂浓度的增大, 费米能级进入价带更深; 光学性质计算表明: 掺杂体系的吸收光谱发生红移, 并在低能区有很强的吸收, 表明掺杂能极大地提高CoCr₂O₄对可见光的吸收和光催化效率。     

Study of graphene device electronic properties with horizontal and vertical double vacancy defects

Abstract

Graphene device electronic properties with double vacancy (DV) defects for two cases, along the direction and perpendicular to the current pathways graphene device, were investigated by using the first principles calculations in combination with density functional theory. The bond lengths, density of states, transmission probability, and current-voltage curves are computed. For relaxed pristine graphene the bond length is around 1.43?Å. However, the bond lengths near the defects for relaxed graphene for DV case are modified to 1.40-1.49?Å. It is also observed that I???V graph is nonlinear based on the current-voltage curve of graphene device which contain DV defects. Furthermore, it has been shown that having the DV defects lead to reduce the current relative to the case of perfect graphene device. Moreover, we noted that when the voltage is increased from zero to one volt new peaks are created near Fermi level in the transmission spectrum graphs. In addition, we noted that the current for the vertical DV defect is smaller than the pristine and horizontal DV device because the number of blocked electrons current pathways in vertical DV defect is larger than the two other cases, namely the pristine and horizontal DV defect cases The obtained results can be useful for the construction of new nanoelectronic devices and may have practical applications.     

Spin‐Polarized Semiconductors: Tuning the Electronic Structure of Graphene by Introducing a Regular Pattern of sp3 Carbons on the Graphene Plane

First‐principles calculations (generalized gradient approximation, density functional therory (DFT) with dispersion corrections, and DFT plus local atomic potential) are carried out on the stability and electronic structures of superlattice configurations of nitrophenyl diazonium functionalized graphene with different coverage. In the calculations, the stabilities of these structures are strengthened significantly since van der Waals interactions between nitrophenyl groups are taken into account. Furthermore, spin‐polarized and wider‐bandgap electronic structures are obtained when the nitrophenyl groups break the sublattice symmetry of the graphene. The unpaired quasi‐localized p electrons are responsible for this itinerant magnetism. The results provide a novel approach to tune graphene's electronic structures as well as to form ferromagnetic semiconductive graphene.     

Correlation between electronic structure, mechanical properties and phase stability in intermetallic compounds

From the detailed electronic structure studies on intermetallic compounds, it has been found that these materials have low heat of formation and large glass-forming ability, if the Fermi level falls on the peak in the density of states (DOS) curve. On the other hand, if theE _F falls on the pseudogap in the DOS curve, the ordering energy will be larger and the system prefers to form an ordered alloy. The first principles electronic structure calculations performed on Ni₃Al show that it is possible to vary the filling of bonding, nonbonding and antibonding states in the DOS curve and this in turn shows gradual structural transformation as well as formation of multiphases by ternary alloying. Possibilities of tailoring the properties of materials by tuning the Fermi level is discussed in this paper.     

Molecular Structure and Electronic Spectra of CoS under the Radiation Fields

We optimized the ground-state stable configuration of CoS molecule in different external radiation fields (0-0.04 atomic units (a.u.)) at the basis set level of 6-311G++ (d, p) using the B3LYP density functional theory. On this basis, the molecular structure, total energy, energy gap, and the intensities of infrared ray (IR) spectra, Raman spectra, and ultraviolet-visible (UV-Vis) absorption spectra of CoS molecule were computed using the same method. The results showed that the molecular structure changed greatly under the effect of the external radiation fields and had significant dependency on the radiation fields. The total energy of CoS molecule grew slightly at first and then significantly decreased in a monotonous manner. The bond length, dipole moment, and energy gap of the molecule all reduced at first and then increased, with the turning point all at F=0.025 a.u. of the radiation field. The absorption peak of IR spectra and Raman optical activity both had maximums at F=0.03 a.u. with significant red shift. In the external radiation field of F=0.030 a.u., the absorption wavelength of the UV-Vis absorption spectra showed large blue shift, and a strong absorption peak was observed.     

Local Electronic Structure of Molecular Heterojunctions in a Single‐Layer 2D Covalent Organic Framework

The synthesis of a single‐layer covalent organic framework (COF) with spatially modulated internal potentials provides new opportunities for manipulating the electronic structure of molecularly defined materials. Here, the fabrication and electronic characterization of COF‐420: a single‐layer porphyrin‐based square‐lattice COF containing a periodic array of oriented, type II electronic heterojunctions is reported. In contrast to previous donor–acceptor COFs, COF‐420 is constructed from building blocks that yield identical cores upon reticulation, but that are bridged by electrically asymmetric linkers supporting oriented electronic dipoles. Scanning tunneling spectroscopy reveals staggered gap (type II) band alignment between adjacent molecular cores in COF‐420, in agreement with first‐principles calculations. Hirshfeld charge analysis indicates that dipole fields from oriented imine linkages within COF‐420 are the main cause of the staggered electronic structure in this square grid of atomically–precise heterojunctions.