Jakob Schiøtz

Softening of nanocrystalline metals at very small grain sizes

Nanocrystalline solids, in which the grain size is in the nanometre range, often have technologically interesting properties such as increased hardness and ductility. Nanocrystalline metals can be produced in several ways, among the most common of which are high-pressure compaction of nanometre-sized clusters and high-energy ball-milling. The result is a polycrystalline metal with the grains randomly orientated. The hardness and yield stress ofthe material typically increase with decreasing grain size, a phenomenon known as the Hall–Petch effect,. Here we present computer simulations of the deformation of nanocrystalline copper, which show a softening with grain size (a reverse Hall–Petch effect,) for the smallest sizes. Most of the plastic deformation is due to a large number of small ‘sliding’ events of atomic planes at the grain boundaries, with only a minor part being caused by dislocation activity in the grains; the softening that we see at small grain sizes is therefore due to the larger fraction of atoms at grain boundaries. This softening will ultimately impose a limit on how strong nanocrystalline metals may become.

Electronic structure calculations with GPAW: A real-space implementation of the projector augmented-wave method

Electronic structure calculations have become an indispensable tool in many areas of materials science and quantum chemistry. Even though the Kohn-Sham formulation of the density-functional theory (DFT) simplifies the many-body problem significantly, one is still confronted with several numerical challenges. In this article we present the projector augmented-wave (PAW) method as implemented in the GPAW program package (https://wiki.fysik.dtu.dk/gpaw) using a uniform real-space grid representation of the electronic wavefunctions. Compared to more traditional plane wave or localized basis set approaches, real-space grids offer several advantages, most notably good computational scalability and systematic convergence properties. However, as a unique feature GPAW also facilitates a localized atomic-orbital basis set in addition to the grid. The efficient atomic basis set is complementary to the more accurate grid, and the possibility to seamlessly switch between the two representations provides great flexibility. While DFT allows one to study ground state properties, time-dependent density-functional theory (TDDFT) provides access to the excited states. We have implemented the two common formulations of TDDFT, namely the linear-response and the time propagation schemes. Electron transport calculations under finite-bias conditions can be performed with GPAW using non-equilibrium Green functions and the localized basis set. In addition to the basic features of the real-space PAW method, we also describe the implementation of selected exchange-correlation functionals, parallelization schemes, ΔSCF-method, x-ray absorption spectra, and maximally localized Wannier orbitals.

Tuning the activity of Pt alloy electrocatalysts by means of the lanthanide contraction

A lanthanide boost for platinum High loadings of precious platinum are needed for automotive fuel cells, because the kinetics of the oxygen reduction reaction (ORR) are relatively slow. Escudero-Escribano et al. studied a series of platinum alloys with lanthanides and alkaline earth elements. When the surfaces were leached to leave pure platinum, they developed compressive strain that boosted the ORR activity—up to a factor of 6 for terbium. Enthalpy effects helped to stabilize these alloys under operating conditions. Science, this issue p. 73 Alloying platinum with lanthanide elements compresses its surface layer and boosts its oxygen reduction activity. The high platinum loadings required to compensate for the slow kinetics of the oxygen reduction reaction (ORR) impede the widespread uptake of low-temperature fuel cells in automotive vehicles. We have studied the ORR on eight platinum (Pt)–lanthanide and Pt-alkaline earth electrodes, Pt5M, where M is lanthanum, cerium, samarium, gadolinium, terbium, dysprosium, thulium, or calcium. The materials are among the most active polycrystalline Pt-based catalysts reported, presenting activity enhancement by a factor of 3 to 6 over Pt. The active phase consists of a Pt overlayer formed by acid leaching. The ORR activity versus the bulk lattice parameter follows a high peaked “volcano” relation. We demonstrate how the lanthanide contraction can be used to control strain effects and tune the activity, stability, and reactivity of these materials.

Wetting/ non-wetting phenomena during catalysis: Evidence from in situ on-line EXAFS studies of Cu-based catalysts

In the present study we have used in situ EXAFS to provide experimental evidence for a reversible change in the morphology of the metallic particles in a high surface area, porous catalyst system, Cu/ZnO, containing small metallic copper particles. By changing the oxidation potential in the synthesis gas mixture, it is found that the apparent Cu-Cu coordination number changes in an essentially reversible manner suggesting that the small metallic Cu particles dynamically change morphology. This indicates that a wetting/non-wetting phenomenon takes place in the Cu/ZnO system with changing partial pressures of oxygen. Under similar conditions, these effects are not observed when copper is supported on, for example, SiO2. A model based on surface and interface free energies provides a simple explanation for the observed results. Since the wetting/non-wetting processes are accompanied by a change in the active surface area, the observed behavior has important general implications and such effects must be incorporated into microkinetic models in order to provide a proper description of the catalyst performance.

Δ self-consistent field method to obtain potential energy surfaces of excited molecules on surfaces

We present a modification of the

Ab initio van der waals interactions in simulations of water alter structure from mainly tetrahedral to high-density-like.

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Electrochemical control of quantum interference in anthraquinone-based molecular switches

self-consistent field (

Robust structural identification via polyhedral template matching

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Hot-electron-mediated desorption rates calculated from excited-state potential energy surfaces

) method of calculating energies of excited states in order to make it applicable to resonance calculations of molecules adsorbed on metal surfaces, where the molecular orbitals are highly hybridized. The

Atomic-scale structure of dislocations revealed by scanning tunneling microscopy and molecular dynamics.

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