27 research outputs found
Probing the Structure and Energetics of Dislocation Cores in SiGe Alloys through Monte Carlo Simulations
We present a methodology for the investigation of dislocation energetics in
segregated alloys based on Monte Carlo simulations which equilibrate the
topology and composition of the dislocation core and its surroundings. An
environment-dependent partitioning of the system total energy into atomic
contributions allows us to link the atomistic picture to continuum elasticity
theory. The method is applied to extract core energies and radii of 60 degrees
glide dislocations in segregated SiGe alloys which are inaccessible by other
methods.Comment: 5 pages, to be published in Physical Review Letter
Softening of ultra-nanocrystalline diamond at low grain sizes
Ultra-nanocrystalline diamond is a polycrystalline material, having
crystalline diamond grains of sizes in the nanometer regime. We study the
structure and mechanical properties of this material as a function of the
average grain size, employing atomistic simulations. From the calculated
elastic constants and the estimated hardness, we observe softening of the
material as the size of its grains decreases. We attribute the observed
softening to the enhanced fraction of interfacial atoms as the average grain
size becomes smaller. We provide a fitting formula for the scaling of the
cohesive energy and bulk modulus with respect to the average grain size. We
find that they both scale as quadratic polynomials of the inverse grain size.
Our formulae yield correct values for bulk diamond in the limit of large grain
sizes.Comment: 5 pages, 3 figures, to be published in Acta Materiali
Dinitrosyl formation as an intermediate stage of the reduction of NO in the presence of MoO_3
We present first-principles calculations in the framework of
density-functional theory and the pseudopotential approach, aiming to model the
intermediate stages of the reduction of NO in the presence of MoO(010). In
particular, we study the formation of dinitrosyl, which proves to be an
important intermediate stage in the catalytic reduction. We find that the
replacement of an oxygen of MoO by NO is energetically favorable, and that
the system lowers further its energy by the formation of (NO). Moreover,
the geometry and charge distribution for the adsorbed dinitrosyl indicates a
metal-oxide mediated coupling between the two nitrogen and the two oxygen
atoms. We discuss the mechanisms for the dinitrosyl formation and the role of
the oxide in the reaction.Comment: 6 pages, 4 figs, RevTeX. To be published in J. Chem. Phy
Shape-Dependent Single-Electron Levels for Au Nanoparticles
The shape of metal nanoparticles has a crucial role in their performance in heterogeneous catalysis as well as photocatalysis. We propose a method of determining the shape of nanoparticles based on measurements of single-electron quantum levels. We first consider nanoparticles in two shapes of high symmetry: cube and sphere. We then focus on Au nanoparticles in three characteristic shapes that can be found in metal/inorganic or metal/organic compounds routinely used in catalysis and photocatalysis. We describe the methodology we use to solve the Schrödinger equation for arbitrary nanoparticle shape. The method gives results that agree well with analytical solutions for the high-symmetry shapes. When we apply our method in realistic gold nanoparticle models, which are obtained from Wulff construction based on first principles calculations, the single-electron levels and their density of states exhibit distinct shape-dependent features. Results for clean-surface nanoparticles are closer to those for cubic particles, while CO-covered nanoparticles have energy levels close to those of a sphere. Thiolate-covered nanoparticles with multifaceted polyhedral shape have distinct levels that are in between those for sphere and cube. We discuss how shape-dependent electronic structure features could be identified in experiments and thus guide catalyst design
Thiolate Adsorption on Au(hkl) and Equilibrium Shape of Large Thiolate-covered Gold Nanoparticles
The adsorption of thiolates on Au surfaces employing density-functional-theory calculations has
been studied. The dissociative chemisorption of dimethyl disulfide (CH3S−SCH3) on 14 different
Au(hkl) is used as a model system. We discuss trends on adsorption energies, bond lengths, and bond
angles as the surface structure changes, considering every possible Au(hkl) with h, k, l ≤ 3 plus
the kinked Au(421). Methanethiolate (CH3S-) prefers adsorption on bridge sites on all surfaces considered;
hollow and on top sites are highly unfavourable. The interface tensions for Au(hkl)-thiolate
interfaces is determined at low coverage. Using the interface tensions in a Wulff construction method,
we construct atomistic models for the equilibrium shape of large thiolate-covered gold nanoparticles.
Gold atoms in a nanoparticle change their equilibrium positions upon adsorption of thiolates towards
shapes of higher sphericity and higher concentration of step-edge atoms.peerReviewe
Interface and Interphase in Polymer Nanocomposites with Bare and Core-Shell Gold Nanoparticles
Metal nanoparticles are used to modify/enhance the properties of a polymer matrix for a broad range of applications in bio-nanotechnology. Here, we study the properties of polymer/gold nanoparticle (NP) nanocomposites through atomistic molecular dynamics, MD, simulations. We probe the structural, conformational and dynamical properties of polymer chains at the vicinity of a gold (Au) NP and a functionalized (core/shell) Au NP, and compare them against the behavior of bulk polyethylene (PE). The bare Au NPs were constructed via a systematic methodology starting from ab-initio calculations and an atomistic Wulff construction algorithm resulting in the crystal shape with the minimum surface energy. For the functionalized NPs the interactions between gold atoms and chemically adsorbed functional groups change their shape. As a model polymer matrix we consider polyethylene of different molecular lengths, from the oligomer to unentangled Rouse like systems. The PE/Au interaction is parametrized via DFT calculations. By computing the different properties the concept of the interface, and the interphase as well, in polymer nanocomposites with metal NPs are critically examined. Results concerning polymer density profiles, bond order parameter, segmental and terminal dynamics show clearly that the size of the interface/interphase, depends on the actual property under study. In addition, the anchored polymeric chains change the behavior/properties, and especially the chain density profile and the dynamics, of the polymer chain at the vicinity of the Au NP