Energetics of Ge addimers on the Si(1 0 0) and Ge(1 0 0) surfaces: a comparative study

The adsorption energetics of Ge dimers on the (1 0 0) surfaces of Ge and Si has been investigated using the first-principles molecular dynamics method. Four high-symmetry configurations have been considered and fully relaxed. The most stable configuration for Ge dimers on Si(1 0 0) is found to be in the trough between two surface dimer rows, oriented parallel to the substrate Si dimers. These results are consistent with recent experimental studies of the system using the scanning tunneling microscopy (STM), and help to clarify some existing controversies on the interpretation of the STM images. In contrast, for Ge dimers on Ge(1 0 0), the most stable configuration is on top of the substrate dimer row.     

Electronic structure of bulk and (0 0 1) surface layers of pyrite FeS2

The electronic structure of bulk and (0 0 1) surface layers of iron pyrite FeS₂ have been calculated using a modern ab initio pseudo-potential method. For the bulk pyrite the calculated lattice constant, position parameter of sulfur, and band gap are in agreement with experimental values. For the (0 0 1) surface it is found that surface states form a conducting band. The conducting band and the conducting band tail of the bulk conduction manifold overlap and the width of the band gap is not influenced by the surface state. The surface states arise mainly from the iron 3d orbitals in the topmost layer with a smaller contribution from the sulfur 3p states. The relaxation of iron and sulfur atoms is found to be greatest in the top most layer. The surface energy is calculated to be equal to 1.063 J/m².     

A cluster approach to hydrogen chemisorption on the GaAs(1 0 0) surface

Chemisorption properties of atomic hydrogen on the Ga-rich GaAs(1 0 0), (2×1) and β(4×2) surfaces are investigated using ab initio self-consistent restricted open shell Hartree–Fock (ROHF) total energy calculations with Hay–Wadt (HW) effective core potentials. The effects of electron correlation have been included using many-body perturbation theory through second order with the exception of β(4×2) symmetry due to computational limitations. The semiconductor surface is modeled by finite sized hydrogen saturated clusters. The effects of surface reconstruction have been investigated in detail. We report on the energetics of chemisorption on the (1 0 0) surface layer, including adsorption beneath the surface layer at an interstitial site, and also report on the possible dimer bond breaking at the bridge site. Chemisorption energies, bond lengths, and charge population analysis are reported for all considered sites of chemisorption.     

Electronic Structure-Dependent Water-Dissociation Pathways of Ruthenium-Based Catalysts in Alkaline H2-Evolution

Ruthenium (Ru)-based catalysts have displayed compelling hydrogen evolution activities, which hold the promising potential to substitute platinum in alkaline H₂-evolution. In the challenging alkaline electrolytes, the water-dissociation process involves multistep reactions, while the profound origin and intrinsic factors of diverse Ru species on water-dissociation pathways and reaction principles remain ambiguous. Here the fundamental origin of water-dissociation pathways of Ru-based catalysts in alkaline media to be from their unique electronic structures in complex coordination environments are disclosed. These theoretical results validate that the modulated electronic structures with delocalization-localization coexistence at their boundaries between the Ru nanocluster and single-atom site have a profound influence on water-dissociation pathways, which push H₂O* migration and binding orientation during the splitting process, thus enhancing the dissociation kinetics. By creating Ru catalysts with well-defined nanocluster, single-atom site, and also complex site, the electrocatalytic data shows that both the nanocluster and single-atom play essential roles in water-dissociation, while the complex site possesses synergistically enhanced roles in alkaline electrolytes. This study discloses a new electronic structure-dependent water-dissociation pathway and reaction principle in Ru-based catalysts, thus offering new inspiration to design efficient and durable catalysts for the practical production of H₂ in alkaline electrolytes.     

Adsorption of the oxygen to the Al (1 1 1) surface

The interaction of the oxygen with the Al (1 1 1) surface is investigated by using the density-functional theory and the pseudopotential technique. We find that the oxygen molecule becomes unstable near the surface, which is induced by the charge transfer from the surface to the molecule. This result suggests that the experimentally observed “hot adatoms” of oxygen is due to the dissociation of the molecule in the area where the direct interaction with the Al atoms is weak.     

Diffusion of clusters down (1 1 1) aluminum islands

The key factor determining nucleation processes and faceting in homoepitaxial growth as well as texture competition is the mobility of adatoms and small clusters across step edges and facets. Using a combination of molecular dynamics and ab initio calculations, we investigate the mechanisms of small clusters (dimer and trimer) diffusion down the aluminum (1 1 1) surface. In this paper we report results of molecular dynamics studies. Our study shows that the clusters dissociate at the step-edge of compact islands. As a result, the clusters diffuse down the step by an exchange mechanism with a small or medium Schwoebel barrier. The mechanism of this down-diffusion/dissociation is discussed and the corresponding energetics are calculated using the molecular statics method. We find a large anisotropy between the barriers at the two types of 1 1 0 oriented steps.     

Anharmonic effects on Be(0 0 0 1): A molecular dynamics study

Using molecular dynamics simulations and a modified analytic embedded atom method (MAEAM), the anharmonic effects of Be(0 0 0 1) surface have been studied in the temperature range from 0 K to 1400 K. The temperature dependence of the interlayer separation, mean square vibrational displacement, phonon frequencies and phonon line width, and layer structure factor are calculated. The obtained results for temperature dependence of interlayer separation and mean square displacement show that the anharmonic effects are small in the temperature range from 0 K to 1100 K. The calculated layer order parameters indicate that Be(0 0 0 1) surface loses its long-range translational order, but do not premelt up to 50 K below the bulk melting point. The surface disordering may result from strongly contracted c/a ratio of Be.     

Magnetism of hexagonal V and Cr monolayers free-standing and adsorbed on Ag(1 1 1)

Using the tight-binding linear muffin-tin orbital (TB–LMTO) method, we study the magnetism of hexagonal V and Cr monolayers (MLs) either free-standing or epitaxially adsorbed on the Ag(1 1 1) surface, by spin-polarized ab initio electronic structure calculations. For free-standing MLs, we carried out calculations as a function of lattice parameter for various magnetic configurations. We found that for the lattice parameter of Ag(1 1 1) surface (5.45 a.u.), the ferrimagnetic and antiferromagnetic states are clearly more stable than the other solutions. This remains to be true for V and Cr MLs on a Ag(1 1 1) surface.     

Molecular dynamics study on vanadium pentoxide

We have studied bulk structure and three low-index surfaces of V₂O₅ using molecular dynamics (MD) simulation. The calculated infra-red (IR) absorption bands of V₂O₅ bulk structure are consistent with the experimental result. The (0 0 1) surface was calculated to be the most stable, small energy difference between the (0 0 1) surface and bulk corresponds their similarity. Atoms with small coordination relax much more than bulk like atoms, they undergo vertical as well as lateral relaxations in order to compensate the missing bonds at the top layer. The driving force which determines the direction of relaxation seems to be the improvement of local environments of the top layer atoms. The vanadyl oxygens exposed to the (0 0 1) and (0 1 0) as well as (1 0 0) surfaces seem to act as active sites in the oxidation process of hydrocarbons.     

二维晃动自然频率与阻尼比系数的试验识别

液体的晃动模态（自然频率、振型与阻尼比系数）是贮液结构设计以及振动控制的重要参数。在液体晃动的模态试验中,需要激发液面的模态运动,但液面的对称模态运动一般比较难以激发出来,使得对称模态参数（特别是阻尼比系数）难以精确识别。本文采用参数激振的方法对矩形、U形和圆形截面容器进行竖向激振,可容易激发出液体表面的前四阶模态(包括对称模态)运动,撤除激励后液体表面按某一特定的振型作自由衰减振动,通过激光测量液体表面波高的自由衰减曲线,从而精确得到液体晃动的自然频率与对应的阻尼比系数,测得晃动频率与理论频率结果吻合良好,表明本文试验识别方法有效。     

矿用扩径式吸能构件吸能防冲特性研究

为增强液压立柱的防冲性能,有效防治煤矿冲击地压,或在一定程度上减小冲击地压事故造成的损失,提出了一种与液压立柱结合使用的扩径式吸能构件。采用理论分析和试验研究方法,对构件吸能防冲特性进行研究,结果表明：轴向压缩下扩径式吸能构件具有非常好的稳定性和可重复性的变形破坏模式,且构件变形后向四周膨胀值仅为薄壁圆管厚度,几乎不占用其它空间。扩径式吸能构件压缩过程中具有较为理想的力-位移曲线。扩径式吸能构件冲程效率不受几何尺寸影响,扩径式防冲构件具有较小的载荷波动系数。理论推导得出了构件吸能防冲评价指标,并与试验结果具有较好吻合,为构件选取提供了理论依据。扩径式防冲构件是较为理想的吸能防冲构件。     

First principles total energy studies of the adsorption of germane on Ge(001)-c(2 × 4)

We perform first principles total energy calculations to study the energetics, and the atomic structure of the adsorption of germane (GeH₄) molecules on the Ge(001)-c(2 × 4) surface. The adsorption of a GeH₄ unit occurs after its dissociation into a germanium trihydride (GeH₃) and a hydrogen atom and a subsequent decomposition into a germanium dihydride (GeH₂) subunit and H atoms. Consequently, we first consider the adsorption of GeH₂ in two different configurations; the on-dimer and the intra-row geometries. Similar to the adsorption of SiH₂ and GeH₂ on Si(001), it is found that the on-dimer site is more stable than the intra-row geometry by 0.13 eV. However, in the adsorption of a GeH₂ fragment together with two H atoms we find that the intra-row geometry is energetically more favorable, again, similar to the adsorption of SiH₂ and GeH₂ (plus two H atoms) on the Si(001) surface.     

Characterization of CuIn1 − xAlxS2 thin films prepared by thermal evaporation

Ingots containing single crystals of the quaternary alloys CuIn_1 − xAl_xS₂ (CIAS) were grown by a horizontal Bridgman method for compositions with x = 0, 0.2 and x = 0.4. (CIAS) thin films were prepared by thermal evaporation technique on to glass substrates. Structural and optical properties of the films were studied in function of the Al content. Band gap, and absorption coefficients were determined from the analysis of the optical spectra (transmittance and reflectance as a function of wavelength) recorded by a spectrophotometer. The samples have direct bandgap energies of 1.95 eV (x = 0), 2.06 eV (x = 0,2) and 2.1 eV (x = 0,4). These optical results were correlated with the structural analysis by X-Ray diffraction.     

Adsorption and dissociation of the O2 on W(111) surface: a density functional theory study

The adsorption and dissociation of O2 molecules on W(111) surface have been studied at the density functional theory (DFT) level in conjunction with the projector augmented wave (PAW) method. All passable dissociation reaction paths of O2 molecule on W(111) surface are considered. The nudged elastic band (NEB) method is applied to locate transition states, and minimum energy pathways (MEP). We find that there is an existing of little barriers for the dissociations reaction of O2 molecule. Ab initio molecular dynamics simulation is also preformed to study the adsorption and dissociation mechanism of O2 molecules on the W(111) surface. Our results indicate that O2 molecule will be dissociated by inclined deposition at temperature of 10 K, but can stable adsorb on top site by normal deposition. The change of bond length and adsorption energy in process of dissociation of O2 molecules on the W(111) surface are also calculated. The O2 coverage effect is also discussed in this paper.     

The entrapment of organic dyes into sol–gel matrix: Experimental results and modeling for photonic applications

To better understand the electronic absorption spectra in the UV–vis region of the methyl red (MR) dye in its anionic, isoelectronic and zwitterionic forms in aqueous solution, high level sequential-Monte Carlo/quantum mechanics (s-MC/QM) methodology was performed and compared to experimental measurements. The theoretical procedure consists in treating the solute–solvent system separately using classical MC simulations to build the MR aqueous solution and then, the MC structures are treated by quantum approaches. Thus, the solvent effects were investigated including on the INDO/CI-S calculations initially the micro and further the first hydration shells. As we excepted the absorption spectra are characterized by a strong band placed in the region of lowest energies. To the basic form we computed shoulders at 434.33 ± 0.09 and 436.34 ± 0.56 nm corresponding to the micro and first hydration shells, respectively. Our experimental measurements display this shoulder at 431 nm. Under acidic forms (isoelectronic and zwitterionic), we computed the red shift in relation to the basic compound. To the isoelectronic structure we found the absorption maximum located at 485.80 ± 0.34 and 480.66 ± 0.67 nm to the micro and first shells, respectively. The experimental prediction of 513 nm is in good agreement with theoretical result. Finally the zwitterionic form we did not obtain a micro layer, therefore we used only the first shell. Our theoretical results are converged to 502.13 ± 0.79 nm in good concordance with the experimental confirmation of 511 nm.

These samples were optically transparent, hard and resistant to dye leaching and to chemical attacks, being promising materials to be used in optical devices.     

Temperature-dependent magnetic behavior of the Fe (1 0 0) surface

We present a theoretical study of the magnetic properties at finite temperature of the ideal (1 0 0) surface of iron. The spin-polarized electronic structure at a given temperature is determined with a self-consistent d-band model Hamiltonian in which correlation effects are included in a temperature-dependent splitting parameter. The demagnetization process is analyzed and compared with previous results and experimental trends, which will serve us as a test. The applicability of the model to the study of other complex systems like supported clusters or surfaces with defects is discussed.     

Observation of metal on Si(0 0 1) by STM/STS and its consideration based on the first principles calculations

Local density of states (LDOS) is obtained by the first principles calculation based on the density functional theory on the Si(0 0 1)2 × 1 surface and on the surface with an Al dimer. At an Al dimer, LDOS has a high intensity in the conduction band region, which cannot be seen on the Si(0 0 1)2 × 1 surface. This tendency is observed in STS measurements as well. The possibility for a microelementary analysis is presented by applying this method to other metal atoms on the Si surface. Furthermore, it is pointed out that STS measurements should be always performed at the same tip-sample separation to obtain reproducible STS spectrums.     

Calculations of (1 1 0) ferromagnetic surface modes: A method of solution

We present a theoretical method for the calculations of (1 1 0) ferromagnetic surface modes in the context of the Heisenberg model with only nearest neighbors interactions. It does not include either relaxation or reconstruction at the surface. The propagating and evanescent spin waves fields in the two-dimensional plane normal to the surface are investigated in this theoretical approach. Emphasis has been laid upon the advantage of handling each displacement field, characterized by its symmetry in particular. Analytic expressions for the bulk and surface equations of motion are also derived in a low-temperature spin wave approximation which enable us to analyze qualitatively the nature of the modes, by observing the response of the energy branches to the variation of structure factors and exchange parameters occurring on the surface. The results are used to calculate the localized modes of spin waves associated with the surface. Numerical examples of the localized modes are given and they are found to exhibit various effects due to the interplay between the bulk and surface modes. It is shown, that under certain circumstances, either one or two branches of surface spin waves may exist. Also the bulk spin fluctuation field as well as the magnetic surface waves, are in qualitative overall agreement with those obtained in the literature by using a Green’s function formalism.     

Cathodoluminescence study in AlxGa1 − xN structures

In this work, we consider a 2D model for calculation of cathodoluminescence in GaN-based structures. This model is developed using an extended generation profile and taking into account the influence of the carrier diffusion process, internal absorption and some radiative recombination processes. First, we have investigated the effect of hole diffusion length and the surface recombination velocity on the CL spectra of GaN sample grown at 800 °C by MOVPE method. Then, we have calculated the dependence of CL intensity from AlGaN alloys as a function of Al content and the electron beam energy.

Results show a red shift of the CL peaks when the beam energy is varied from 2 to 10 keV at room temperature. The band-edge emission of Al_xGa_1 − xN shifts about 0.49 eV when the Al composition is increased from x = 0.18 to 0.38. Comparison of the experimental spectra with simulations shows a good agreement.     

External Fields Assisted Highly Efficient Oxygen Evolution Reaction of Confined 1T-VSe2 Ferromagnetic Nanoparticles (Small 38/2023)

As a clean and effective approach, the introduction of external magnetic fields to improve the performance of catalysts has attracted extensive attention. Owing to its room-temperature ferromagnetism, chemical stability, and earth abundance, VSe₂ is expected to be a promising and cost-effective ferromagnetic electrocatalyst for the accomplishment of high-efficient spin-related OER kinetics. In this work, a facile pulsed laser deposition (PLD) method combined with rapid thermal annealing (RTA) treatment is used to successfully confine monodispersed 1T-VSe₂ nanoparticles in amorphous carbon matrix. As expected, with external magnetic fields of 800 mT stimulation, the confined 1T-VSe₂ nanoparticles exhibit highly efficient oxygen evolution reaction (OER) catalytic activity with an overpotential of 228 mV for 10 mA cm⁻² and remarkable durability without deactivation after >100 h OER operation. The experimental results together with theoretical calculations illustrate that magnetic fields can facilitate the surface charge transfer dynamics of 1T-VSe₂, and modify the adsorption-free energy of *OOH, thus finally improving the intrinsic activity of the catalysts. This work realizes the application of ferromagnetic VSe₂ electrocatalyst in highly efficient spin-dependent OER kinetics, which is expected to promote the application of transition metal chalcogenides (TMCs) in external magnetic field-assisted electrocatalysis.