Structural relaxation in charged metal surfaces and cluster ions

Space-charge layers can noticeably affect the properties of metal electrode surfaces, for instance by modifying the surface dielectric response or indirectly via the induced atomic relaxations. While there are efforts to exploit this concept for designing novel functional nanomaterials, the underlying microscopic processes are poorly understood. Here, we report on a density functional theory (DFT) study of atomic relaxation in Au cluster ions comprising up to 309 atoms. Suitable averages over atomic displacements respond to charging consistent with experimental observation on macroscopic Au single-crystal surfaces. Moreover, the overall DFT response is also consistent with predictions of a simple phenomenological model. Motivated by our observations, we propose a scenario in which the surface relaxation ("stretch") results from out-of-plane Hellman-Feynman forces exerted on the surface atoms by the excess charge, and where the in-plane surface stress represents essentially an elastic transverse contraction tendency of the surface layer in response to stretch.     

Application of energy density theory on finite cracked bodies

Abstract

A new concept of the energy release rate of a finite cracked body is proposed. Considering the global view of the strain energy density field, the new fracture parameter presented here is different from the conventional energy release rate that only depends on the stress field around the crack tip but neglects the influences induced by the boundary conditions on the far field. Based on the hypothesis of the energy density theory, fracture initiation and termination, respectively can be predicted by the local and global relative minima of the strain energy density function. The new energy release rate is then defined as the integration of the strain energy density along the fracture trajectory from the initiation point to the destination point. The results show that the difference between the new and the conventional energy release rate becomes more pronounced if the material has a large core region (or the material is more ductile) and if the height‐width ratio of a finite cracked plate is comparatively small.     

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.     

半导体非线性光学材料的第一性原理研究

通过第一性原理研究Ⅱ-Ⅳ-Ⅴ2族CKP半导体中的CdSiAs2，计算了其双折射性，量化了双折射性同应力的线性关系，它的负双折射性使之能够通过应力、温度调节以及同CdGeAs2混合来设计非临界位相匹配材料。计算显示，少量的参杂Ge（ 〈5％），能够实现非临界位相匹配I类二次谐波产生（SHG）在CO2激光谱线范围可调谐，它可能具有很高的有效χ^（2）。     

Identifying multiple configurations of complex molecules on metal surfaces

E xperimental identification of molecular configurations in diffusion processes of large complex molecules has been a demanding topic in the field of molecular construction at solid surfaces. Such identification is needed in order to control the self‐assembly process and the properties and configurations of the resulting structures. This paper provides an overview of state‐of‐the‐art techniques for identification of molecular configurations in motion. First, a brief introduction to the conventional tools is presented, for example, low‐energy electron diffraction and IR/Raman spectroscopy. Second, currently used techniques, scanning probe microscopy, and its application in molecular configuration identification are reviewed. In the last part, a methodology combining time‐resolved tunneling spectroscopy and density functional theory calculation is reviewed in detail; this strategy has been successfully applied to two typical molecular systems, (t‐Bu)₄‐ZnPc and FePc (where Pc is phthalocyanine), with molecular rotation and laterial diffusion on the Au(111) surface.     

Interfacial interactions in clay-based nylon 6 nanocomposites: A density functional theory study

Density functional theory was used to study the interfacial interactions between clay and polymer in polymer/clay nanocomposites, with a focus on nylon 6 matrix. The binding energy and the distance between nylon 6 and clay surface were predicted. The effect of the isomorphic substitution in clay octahedral and tetrahedral layer on the strength of the interfacial interactions was also examined. The interaction strength between nylon 6 and clay surface was found to increase with the degree of isomorphic substitution. And the magnitude of the binding forces, reflected from the calculated binding energies, was found to be higher when the substitution took place in tetrahedral layer (e.g., Al³⁺ for Si⁴⁺). No covalent bonds were observed between nylon 6 and the clay, which means that the chemical structures of the clay and nylon 6 are unchanged during the mixing process.     

Adsorption of benzene on noble metal surfaces studied by density functional theory with Van der Waals correction

We have studied the atomic geometries and the electronic properties of benzene/metal interfaces by using density functional theoretical (DFT) calculations with van der Waals corrections. Adsorption energies of benzene on Cu(111), Ag(111), and Au(111) surfaces calculated by van der Waals density functional proposed by Dion and co-workers agree reasonably well with experimentally reported values, while those calculated by a semi-empirical van der Waals correction proposed by Grimme are overestimated slightly. The work function change induced by benzene adsorption on the three surfaces are quite well reproduced by the semi-empirical correction, suggesting that weak adsorption geometries can be quite well reproduced by DFT with a semi-empirical dispersion correction scheme.     

闪锌矿Ga1-xCrxN铁磁性的密度泛函理论

采用基于密度泛函的第一性原理方法计算了闪锌矿GaN掺Cr的电子结构和磁性.考虑不同掺杂浓度和位置,计算结果表明,Ga1-xCrxN呈现铁磁基态,Cr原子间是铁磁性耦合并团簇于N原子,Cr原子与最近邻N原子为反铁磁性耦合.我们采用双交换机制解释了磁性来源和机制.计算结果和最近闪锌矿GaN掺Cr的实验结果吻合.     

SrTiO3材料中氧空位的密度泛函理论

计算了SrTiO3-δ（δ=0，δ=0．125）体系电子结构，分析了氧空位对SrTiO3晶体的价键结构、能带、态密度、分波态密度、差分电荷密度的影响。所有计算都是基于密度泛函理论（DFT）框架下的第一性原理平面波超软赝势方法。计算结果表明：当氧空位浓度δ=0．125时，空位在母体化合物SrTiO3中引入了大量的传导电子，费米能级进入导带，体系显示金属型导电性。由于空位掺杂，导带底附近的态密度发生了畸变，刚性能带模型不再适合描述SrTiO2.875体系。同时，在导带底附近距离费米能级0．3eV处引入了空位能级，这和实验测得的SrTiO3材料内中性氧空位的电离能约为0．4eV相符。此外，Mulliken布局分析、分波态密度和差分电荷密度分析表明，该空位能级主要由与其最近邻的两个Ti原子的3d电子态贡献，并且由该空位引入的导电电子大部分都局域在空位最近邻的两个Ti原子周围。最后，计算了三种典型平衡条件下SrTiO3晶体内中性氧空位的形成能。     

Structural and electronic properties of Ti-nanowires/C-single wall nanotubes composites by density functional theory calculations

Structural and electronic properties of composite Ti-nanowires/single wall carbon nanotubes ((6,0) and (10,0)) (SWNT) were evaluated by means of density functional theory computations. We considered the cases of monoatomic (MNW), BCC (β-NW) and HCP (α-NW) nanowires that were either inserted or deposited in/on the SWNTs. In all cases the NWs turn the cylindrical SWNTs’ shape to ellipsoid, an effect that is closely related to charge transfer from Ti toward C neighboring atoms. We found that the wires inside the SWNT appear to be more stable compared to the outside cases, while all NWs contribute with new energy states at the Fermi level, transforming the semiconducting (10,0) to a conducting composite. In addition, we found spin up–down differences in the β-NW_on case and electronic charge redistributions e.g. in α-NW_in (charge accumulation internally along the tube's axis) or in α-NW_on (superficial charge accumulation in the vicinity of the NW), accompanied by manifestation of electric dipole moment that reaches the value of 10 Debye in a-NW_on. These results may be of use in the design of new C-based nanocomposite systems suitable for applications in microelectronics, sensors and catalysis.     

Mechanical and electronic properties of C60 under structure distortion studied with density functional theory

B3PW91/6-31G density functional method was employed to investigate the elastic, strength and electronic properties of C₆₀(I_h) in its ground electronic state (X ¹A_g). Most of the properties were examined for larger structure distortions. The over-all elastic constant were derived from the near-equilibrium potential energy curves (PECs) in five independent directions [according to symmetries by 1. D_5d, 2. D_3d, 3. D_2h, 4. C_2h(1), 5. C_2h(2)]. By extension of the distortions as large as the structure of C₆₀ was destroyed, the necessary energies were obtained, which quantitatively illuminated the stability of C₆₀ theoretically. Analytical polynomial fit of the full PECs reproduced the energy data accurately. Time-dependent B3PW91/6-31G analysis showed significant electronic spectra changes associated with the structure distortions. Elongation in the direction of D_5d and compression in that of D_2h encountered potential energy surface cross-linkages, which might be considered as a single electron pump for further application in designs of single electron devices.     

Direct imaging of molecular orbitals of metal phthalocyanines on metal surfaces with an O2-functionalized tip of a scanning tunneling microscope

High-resolution scanning tunneling microscope images of iron phthalocyanine and zinc phthalocyanine molecules on Au(111) have been obtained using a functionalized tip of a scanning tunneling microscope (STM), and show rich intramolecular features that are not observed using clean tips. Ab initio density functional theory calculations and extended Hückel theory calculations revealed that the imaging of detailed electronic states is due specifically to the decoration of the STM tip with O₂. The detailed structures are differentiated only when interacting with the highly directional orbitals of the oxygen molecules adsorbed on a truncated, [111]-oriented tungsten tip. Our results indicate a method for increasing the resolution in generic scans and thus, have potential applications in fundamental research based on high-resolution electronic states of molecules on metals, concerning, for example, chemical reactions, and catalysis mechanisms.     

Fe Nanoclusters on the Ge（001） Surface Studied by Scanning Tunneling Microscopy,Density Functional Theory Calculations and X-Ray Magnetic Circular Dichroism

The growth of Fe nanoclusters on the Ge(001) surface has been studied using low-temperature scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. STM results indicate that Fe nucleates on the Ge(001) surface, forming well-ordered nanoclusters of uniform size. Depending on the preparation conditions, two types of nanoclusters were observed having either four or sixteen Fe atoms within a nanocluster. The results were confirmed by DFT calculations. Annealing the nanoclusters at 420 K leads to the formation of nanorow structures, due to cluster mobility at such temperature. The Fe nanoclusters and nanorow structures formed on the Ge(001) surface show a superparamagnetic behaviour as measured by X-ray magnetic circular dichroism.      

Ab initio tensile testing simulation of aluminum and aluminum nitride ceramics based on density functional theory

The ideal strength and mechanical behavior of aluminum, aluminum nitride, and their composites at zero temperature are investigated using ab initio norm conserving pseudopotential methods based on local density approximation. The total energy and stress of supercells which contain these atomistic models are calculated under uniaxial tensile strain. Estimated various physical properties of aluminum and aluminum nitride at equilibrium state are in good agreement with the experiment. The tensile test of the composite model shows a failure of the composite in the aluminum matrix. The ideal strength of these models is also estimated.     

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.     

Stability of fcc (1 1 0) transition and noble metal surfaces

We have used density functional theory in conjunction with the full charge density linear muffin-tin orbitals method and a cluster expansion based on interatomic pair potentials to derive the energetics of vicinal surfaces on transition and noble metals, and we apply the results in a study of the stability of the fcc (1 1 0) facet of these metals against the formation of ‘rippled' surfaces consisting of vicinal facets with Miller indices (2λ+1,2λ+1,1) and .     

Two-dimensional square transition metal dichalcogenides with lateral heterostructures

Fabrication of lateral heterostructures (LHS) is promising for a wide range of next-generation devices and could sufficiently unlock the potential of two-dimensional materials.Herein,we demonstrate the design of lateral heterostructures based on new building materials,namely 1S-MX2 LHS,using first-principles calculations.1S-MX2 LHS exhibits excellent stability,demonstrating high feasibility in the experiment.The desired bandgap opening can endure application at room temperature and was confirmed in 1S-MX2 LHS with spin-orbit coupling (SOC).A strain strategy further resulted in efficient bandgap engineering and an intriguing phase transition.We also found that black phosphorus can serve as a competent substrate to support 1S-MX2 LHS with a coveted type-Ⅱ band alignment,allowing versatile functionalized bidirectional heterostructures with built-in device functions.Furthermore,the robust electronic features could be maintained in the 1S-MX2 LHS with larger components.Our findings will not only renew interest in LHS studies by enriching their categories and properties,but also highlight the promise of these lateral heterostructures as appealing materials for future integrated devices.     

Structural evolution of clusters using genetic algorithm and density functional theory method

Structural evolution of clusters have been studied using an extensive, unbiased search based on genetic algorithm and density functional theory (DFT) methods. Cationic, neutral, and anionic silver clusters have planar shapes for their lowest-energy structures up to n = 7, 6, and 6, respectively. Most of the competitive candidates for are found to adopt close-flat configurations. The present results obtained by employing the Perdew–Wang 91 (PW91) exchange-correlation functional are significantly different from those predicted in earlier work using empirical and semi-empirical potentials, and partly in line with the previous first-principles calculations. The dependences of the lowest-energy structures of on second finite differences of total energy, binding energies per atom, highest occupied and lowest unoccupied molecular orbital energy gaps, ionization potentials, and electron affinities are studied in detail. The calculated ionization potentials and electron affinities of the optimal clusters display distinct even–odd oscillations. The neutral Ag clusters with 6-, 8-, and 14-atoms are suggested to be “magic” clusters by an analysis of their geometric and electronic properties.     

CoSb2结构5d过渡金属二氮化物力学性质的第一性原理研究

基于密度泛函理论平面波赝势的第一性原理方法,对具有CoSb2结构5d过渡金属二氮化物TMN2(TM=Hf、Ta、w、Re、Os、Ir、Pt、Au)的晶格常数、电子结构和力学性能进行了计算.计算结果表明,对于该结构的二氮化物,除AuN2外,均同时满足热力学和机械稳定性标准;其中OsN2具有最高的体弹性模量和剪切模量分别为418和257GPa;态密度分析表明,过渡金属原子的5d轨道与氮原子的2p轨道之间发生了强烈的杂化现象,二者之间形成了较强共价键.