Gapped ferromagnetic graphene nanoribbons

We theoretically design a graphene-based all-organic ferromagnetic semiconductor by terminating zigzag graphene nanoribbons (ZGNRs) with organic magnets. A large spin-split gap with a 100% spin polarized density of states near the Fermi energy is obtained, which is of potential application in spin transistors. The interactions among electron, spin and lattice degrees of freedom are studied using the first-principles calculations including non-collinear spin orientations. All of the calculations consistently demonstrate that although no d electrons existing, the antiferromagnetic π-π exchange together with the strong electron-lattice interactions between organic magnets and ZGNRs make the ground state ferromagnetic.     

Suppression of field emission from W(110) and W(111) by Cu overlayers

The total energy distribution and the Fowler-Nordheim preexponential factor have been measured for field emission from the (100) and (111) facets of tungsten in the absence and in the presence of overlayers of chemisorbed copper. It is found that at close to monolayer coverage on the (100) facet the adsorbate dramatically reduces the surface density of states at the Fermi energy, whereas on the (111) facet the surface density of states at the Fermi energy is little affected. Self-consistent, semirelativistic LMTO calculations of the k-resolved layer densities of states at the centre of the surface Brillouin zone have been carried out for a tungsten-vacuum interface with and without an ordered overlayer of copper. According to the calculations, a copper monolayer on W(100) strongly suppresses the surface density of states at the Fermi energy, whereas for a copper monolayer on W(111) no such suppression is predicted. The consistency of these results with the experimental data indicates the promise of the present method for calculating the electronic structures of metal-vacuum interfaces.     

Electron transport through single conjugated organic molecules: basis set effects in ab initio calculations

We investigate electron transport through single conjugated molecules--including benzenedithiol, oligophenylene ethynylenes of different lengths, and a ferrocene-containing molecule sandwiched between two gold electrodes with different contact structures--by using a single-particle Green function method combined with density functional theory calculation. We focus on the effect of the basis set in the ab initio calculation. It is shown that the position of the Fermi energy in the transport gap is sensitive to the molecule-lead charge transfer which is affected by the size of basis set. This can dramatically change, by orders of magnitude, the conductance for long molecules, though the effect is only minor for short ones. A resonance around the Fermi energy tends to pin the position of the Fermi energy and suppress this effect. The result is discussed in comparison with experimental data.     

Cs的覆盖度对Cs/石墨烯的结构稳定性和场发射性能影响

采用密度泛函理论方法,对Cs以不同覆盖度吸附在石墨烯表面时系统的结构稳定性和场发射性能进行了研究.计算结果表明单原子Cs吸附在石墨烯表面的碳六元环的中心位置时系统的能量最低.随着Cs的覆盖度增加,碱金属Cs与石墨烯之间的吸附作用逐渐增强,(4×4)R 0°和(2×2)R 0°结构是稳定的.由于碱金属Cs的修饰作用,Cs/石墨烯体系的功函明显下降,且随着碱金属Cs的覆盖度增大,系统的功函逐渐减小.态密度的计算结果表明功函的下降主要与Cs和石墨烯之间的电子转移有关.随着覆盖度的增大,石墨烯的电子态逐渐向低能方向移动,系统的费米能级升高并导致材料的功函下降.     

Cs的覆盖度对Cs/石墨烯的结构稳定性和场发射性能影响

采用密度泛函理论方法,对Cs以不同覆盖度吸附在石墨烯表面时系统的结构稳定性和场发射性能进行了研究。计算结果表明单原子Cs吸附在石墨烯表面的碳六元环的中心位置时系统的能量最低。随着Cs的覆盖度增加,碱金属Cs与石墨烯之间的吸附作用逐渐增强,(4×4)R 0°和(2×2)R 0°结构是稳定的。由于碱金属Cs的修饰作用,Cs/石墨烯体系的功函明显下降,且随着碱金属Cs的覆盖度增大,系统的功函逐渐减小。态密度的计算结果表明功函的下降主要与Cs和石墨烯之间的电子转移有关。随着覆盖度的增大,石墨烯的电子态逐渐向低能方向移动,系统的费米能级升高并导致材料的功函下降。     

Positron annihilation and constant photocurrent method measurements on a-Si:H films: A comparative approach to defect identification

Defect structure of hydrogenated amorphous silicon thin-films was studied by positron annihilation spectroscopy (PAS), whereas the density of states below the Fermi level was measured by constant photocurrent method (CPM). Divacancies and large vacancy clusters were identified as the main defects present in these films, with relative concentrations strongly dependent on the rf-power. Correlation between PAS, CPM results and I(V) characteristics of solar cells suggests the creation of energy levels above the Fermi energy, not observable by CPM, related to large vacancy clusters.     

Determining Seebeck coefficient of heavily doped La:SrTiO3 from density functional calculations

A novel approach was developed to calculate temperature-dependent Seebeck coefficient of heavily doped systems. The electronic density of states (DOS) and Fermi energy were determined and then, using these two parameters, the Seebeck coefficient was calculated by using Boltzmann transport theory. This approach is applied to heavily La-doped SrTiO₃. The calculated Seebeck coefficient agrees well with the experimental data. By analyzing the results, it was shown that Seebeck coefficient is greatly affected by the asymmetry of DOS with respect to Fermi energy.     

Field emission properties of N-doped capped single-walled carbon nanotubes: a first-principles density-functional study

The geometrical structures and field emission properties of pristine and N-doped capped (5,5) single-walled carbon nanotubes have been investigated using first-principles density-functional theory. The structures of N-doped carbon nanotubes are stable under field emission conditions. The calculated work function of N-doped carbon nanotube decreases drastically when compared with pristine carbon nanotube, which means the enhancement of field emission properties. The ionization potentials of N-doped carbon nanotubes are also reduced significantly. The authors analyze the field emission mechanism in terms of energy gap between the lowest unoccupied molecular orbital and the highest occupied molecular orbital, Mulliken charge population, and local density of states. Due to the doping of nitrogen atom, the local density of states at the Fermi level increases dramatically and donor states can be observed above the Fermi level. The authors' results suggest that the field emission properties of carbon nanotubes can be enhanced by the doping of nitrogen atom, which are consistent with the experimental results.     

Correlation between electronic properties and hydrodesulfurization activity of 4d-transition-metal sulfides

The present study attempts to examine the relationship between electronic-structure properties exhibited by 4d-transition-metal sulfides (TMSs) in connection with the hydrodesulfurization (HDS) catalytic activity. The electronic structure is studied by means of a periodic density functional approach using a plane-wave basis set and appropriate pseudopotentials. Both bulk and relevant surfaces of NbS, NbS(2), MoS(2), TcS(2), RuS(2), Rh(2)S(3), PdS, and PdS(2) have been analyzed. High densities of nonbonding states below the Fermi level have been found for the TMSs that exhibit good catalytic performance. Therefore, it is suggested that the incomplete filling of the band gap at exposed transition metal atoms over the catalyst surface plays a determinant role in the HDS reactions. It has also been found that the highest HDS activity occurs when the surface-metal-site density of electronic states has a local minimum at the Fermi level that enhances the donation-back-donation mechanism. Additionally, the Sabatier principle is qualitatively rationalized in terms of the position of covalent bands below the Fermi level.     

Photofield emission spectroscopy

A brief review of the investigations of optical excitations in the bulk and on the surfaces of metals by the photofield emission method is presented. The selected results show that the method is very useful for detailed penetration of band structure near the Fermi level. Examples for bulk band structures and surface density of states of tungsten, tantalum and titanium are presented and compared with theoretical results. The residual gas effect on surface states is described and discussed. Taking into consideration the thermocurrent produced by light radiation, a new and more detailed presentation of surface states observed for titanium (0001) face is shown as the density of states. The method of energy distribution of photofield emitted electrons is briefly mentioned. The inverse and two-photon photoemission methods are mentioned.     

氢分子在ZrC(111)面解离过程的动态能带结构研究

采用密度泛函方法和平板模型对H₂在ZrC(111)面上的反应途径进行了研究, 结果表明H₂在该表面上的解离易于发生. 通过考察各中间态的能带结构, 在H₂解离的过程中, H 1s诱导态(占据)所处能量位置存在着先上升后下降的过程, 同时清洁表面中处在费米能级下方的以表面Zr原子4d_xz/d_yz为主要成分的能带消失. 上述能带结构分析结果再现了活性表面态在反应过程中的作用, 并与光电子能谱观测结果相吻合.     

Ab Initio Studies of Ag-S Bond Formation during the Adsorption of l-Cysteine on Ag(111)

Ab initio studies of Ag-S bond formation during the adsorption of l-cysteine on Ag(111) have been performed by combining density functional theory with a quantum mechanical model developed in our group. The adsorbate-silver bond formation has been investigated by analyzing the projected density of states onto the different atoms of the molecule and by charge density difference calculations when the zwitterion radical approaches the surface. The polar character of the bond can be distinguished. For the first time, the coupling constants of the sulfur orbitals with the d and sp bands have been calculated by fitting the density of states. The role of the sp bands in the stabilization of the sulfur-silver bond is analyzed. The differences with the catalysis of hydrogen adsorption are discussed. Copper, gold, and silver are not good catalysts for the adsorption of hydrogen because of the position of the d bands lying too far below the Fermi level. However, the coin metals are excellent for the adsorption of thiols. The reason is that at the equilibrium position the sulfur atom is much farther from the surface than hydrogen, and thus the interactions with the sp bands stabilize its bond to the surface.     

Interpretation of electron diffusion coefficient in organic and inorganic semiconductors with broad distributions of states

The carrier transport properties in nanocrystalline semiconductors and organic materials play a key role for modern organic/inorganic devices such as dye-sensitized (DSC) and organic solar cells, organic and hybrid light-emitting diodes (OLEDs), organic field-effect transistors, and electrochemical sensors and displays. Carrier transport in these materials usually occurs by transitions in a broad distribution of localized states. As a result the transport is dominated by thermal activation to a band of extended states (multiple trapping), or if these do not exist, by hopping via localized states. We provide a general view of the physical interpretation of the variations of carrier transport coefficients (diffusion coefficient and mobility) with respect to the carrier concentration, or Fermi level, examining in detail models for carrier transport in nanocrystalline semiconductors and organic materials with the following distributions: single and two-level systems, exponential and Gaussian density of states. We treat both the multiple trapping models and the hopping model in the transport energy approximation. The analysis is simplified by thermodynamic properties: the chemical capacitance, C(mu), and the thermodynamic factor, chi(n), that allow us to derive many properties of the chemical diffusion coefficient, D(n), used in Fick's law. The formulation of the generalized Einstein relation for the mobility to diffusion ratio shows that the carrier mobility is proportional to the jump diffusion coefficient, D(J), that is derived from single particle random walk. Characteristic experimental data for nanocrystalline TiO(2) in DSC and electrochemically doped conducting polymers are discussed in the light of these models.     

稀土对ZA27合金晶间腐蚀影响的电子理论研究

通过自行开发的计算机软件构造了ZA27合金中α相大角度晶界析出η相及稀土元素的原子集团模型. 采用递归法计算了Al, Zn, La, Y的局域态密度, 计算并分析了α相、η相的总态密度和费米能级, 及稀土对态密度和费米能级的影响. 计算表明: 稀土元素的局域态密度形状与Zn相近, 其与Zn结合的能力大; 稀土元素降低η相的费米能级, 减小Zn, Al电极电位差, 具有抑制晶间腐蚀的作用; 稀土元素不改变α相、η相的总态密度形状, 但使η相的态密度增大, 改变η相的电子结构; 晶格结构对原子的态密度有一定的影响, 掺杂原子的态密度趋于与基体原子态密度相同.     

纳米碳管电子结构和键合特性的第一原理研究

利用第一原理方法对一系列尺寸变化的单层纳米碳管电子结构进行了研究,得到了总态密度和态密度随碳管半径R的变化情况与实验结果完全一致,Fermi能级处态密度值随着管径R的增大而减小,说明纳米管的化学活性随着管径的增大而增强。碳管中C-C之间的键合为2s和2p价电子混合而成的弯曲的σ,π键,随着管径R的增大,化学键的弯曲度逐渐减小,C-C之间的键合作用和结合能逐渐增强,电荷密度和对应的势场也逐渐减弱。这些结果表明管径较小的纳米碳管在复合材料的合成中具有一定的优势。     

The high-pressure electronic structure of the [Ni(ptdt)2] organic molecular conductor

The electronic structure of the single component molecular crystal [Ni(ptdt)(2)] (ptdt = propylenedithiotetrathiafulvalenedithiolate) is determined at ambient and high pressure using density functional theory. The electronic structure of this crystal is found to be of the "crossing bands" type with respect to the dispersion of the HOMO and LUMO, resulting in a small, non-zero density of states at the Fermi energy at ambient pressure, indicating that this crystal is a "poor quality" metal, and is consistent with the crystal's resistivity exhibiting a semiconductor-like temperature dependence. The ambient pressure band structure is found to be predominantly one-dimensional, reflecting enhanced intermolecular interactions along the [100] stacking direction. Our calculations indicate that the band structure becomes two-dimensional at high pressures and reveals the role of shortened intermolecular contacts in this phenomenon. The integrity of the molecular structure is found to be maintained up to at least 22 GPa. The electronic structure is found to exhibit a crossing bands nature up to 22 GPa, where enhanced intermolecular interactions increase the Brillouin zone centre HOMO-LUMO gap from 0.05 eV at ambient pressure to 0.15 eV at 22 GPa; this enhanced HOMO-LUMO interaction ensures that enhancement of a metallic state in this crystal cannot be simply achieved through the application of pressure, but rather requires some rearrangement of the molecular packing. Enhanced HOMO-LUMO interactions result in a small density of states at the Fermi energy for the high pressure window 19.8-22 GPa, and our calculations show that there is no change in the nature of the electronic structure at the Fermi energy for these pressures. We correspondingly find no evidence of an electronic semiconducting-metal insulator transition for these pressures, contrary to recent experimental evidence [Cui et al., J. Am. Chem. Soc. 131, 6358 (2009)].     

Effect of high hydrostatic pressure on structural stability of Ti3GeC2: A first-principles investigation

An investigation into the structural stability, electronic and elastic properties of Ti₃GeC₂ under high hydrostatic pressure was conducted using first-principles calculations based on density functional theory (DFT). From the energy and enthalpy calculations, and the variations of elastic constants with pressure, we conclude that α‐Ti₃GeC₂ is most stable upon compression to 100 GPa, which is not consistent with the nonhydrostatic in situ synchrotron X-ray diffraction studies. The higher structural stability was analyzed in terms of electronic level. The absence of band gap at the Fermi level and the finite value of the density of states at the Fermi energy reveal the metallic behavior of all polymorphs of Ti₃GeC₂.     

C36填充单壁碳纳米管的结构和电子性质

The structures and electronic properties for C36 encapsulated in four single-wall armchair carbon nanotubes (C36@(n,n), n=6-9) were calculated using ab initio self-consistent field crystal orbital method based on density functional theory. The calculations show that the interwall spacing between the carbon nanotube and C36 plays an important role in the stabilities of resultant structures. The optimum interwall spacing is about 0.30 nm and the tubes can be considered as inert containers for the encapsulated C36. The Fermi levels and relative position of energy bands also have something to do with the interwall spacing. The shifts of Fermi level and C36-derived electron states modulate the electron properties of these structures. The extra electrons fill the bands of C36@(8,8) with the optimum interwall spacing almost in a rigid-band manner.     

Electron momentum density and band structure calculations of α- and β-GeTe

We have measured isotropic experimental Compton profile of α-GeTe by employing high energy (662 keV) γ-radiation from a ¹³⁷Cs isotope. To compare our experiment, we have also computed energy bands, density of states, electron momentum densities and Compton profiles of α- and β-phases of GeTe using the linear combination of atomic orbitals method. The electron momentum density is found to play a major role in understanding the topology of bands in the vicinity of the Fermi level. It is seen that the density functional theory (DFT) with generalised gradient approximation is relatively in better agreement with the experiment than the local density approximation and hybrid Hartree–Fock/DFT.