First-principles kinetic Monte Carlo simulations for heterogeneous catalysis, applied to the CO oxidation at RuO2(110)

We describe a first-principles statistical mechanics approach enabling us to simulate the steady-state situation of heterogeneous catalysis. In a first step density-functional theory together with transition-state theory is employed to obtain the energetics of all relevant elementary processes. Subsequently the statistical mechanics problem is solved by the kinetic Monte Carlo method, which fully accounts for the correlations, fluctuations, and spatial distributions of the chemicals at the surface of the catalyst under steady-state conditions. Applying this approach to the catalytic oxidation of CO at RuO2(110), we determine the surface atomic structure and composition in reactive environments ranging from ultra-high vacuum (UHV) to technologically relevant conditions, i.e. up to pressures of several atmospheres and elevated temperatures. We also compute the CO2 formation rates (turnover frequencies). The results are in quantitative agreement with all existing experimental data. We find that the high catalytic activity of this system is intimately connected with a disordered, dynamic surface ``phase'' with significant compositional fluctuations. In this active state the catalytic function results from a self-regulating interplay of several elementary processes.Comment: 18 pages including 9 figures; related publications can be found at http://www.fhi-berlin.mpg.de/th/th.htm

Origins of conductance anomalies in a p-type GaAs quantum point contact

Low temperature transport measurements on a p-GaAs quantum point contact are presented which reveal the presence of a conductance anomaly that is markedly different from the conventional `0.7 anomaly'. A lateral shift by asymmetric gating of the conducting channel is utilized to identify and separate different conductance anomalies of local and generic origins experimentally. While the more generic 0.7 anomaly is not directly affected by changing the gate configuration, a model is proposed which attributes the additional conductance features to a gate-dependent coupling of the propagating states to localized states emerging due to a nearby potential imperfection. Finite bias conductivity measurements reveal the interplay between the two anomalies consistently with a two-impurity Kondo model

Comparison of the full-potential and frozen-core approximation approaches to density-functional calculations of surfaces

We scrutinize the accuracy of the pseudopotential approximation in density-functional theory (DFT) calculations of surfaces by systematically comparing to results obtained within a full-potential setup. As model system we choose the CO oxidation at a RuO2(110) surface and focus in particular on the adsorbate binding energies and reaction barriers as target quantities for the comparison. Rather surprisingly, the major reason for discrepancy does not result from the neglected semi-core state relaxation in the frozen-core approximation, but from an inadequate description of the local part of the Ru pseudopotential, responsible for the scattering of f like waves. Tiny, seemingly irrelevant, imprecisions appearing in these properties can have a noticeable influence on the surface energetics. At least for the present example, we obtain excellent agreement between both approaches, if the pseudopotential describes these scattering properties accurately.Comment: 8 pages including 3 figures; related publications can be found at http://www.fhi-berlin.mpg.de/th/th.htm

Metastable precursors during the oxidation of the Ru(0001) surface

Using density-functional theory, we predict that the oxidation of the Ru(0001) surface proceeds via the accumulation of sub-surface oxygen in two-dimensional islands between the first and second substrate layer. This leads locally to a decoupling of an O-Ru-O trilayer from the underlying metal. Continued oxidation results in the formation and stacking of more of these trilayers, which unfold into the RuO_2(110) rutile structure once a critical film thickness is exceeded. Along this oxidation pathway, we identify various metastable configurations. These are found to be rather close in energy, indicating a likely lively dynamics between them at elevated temperatures, which will affect the surface chemical and mechanical properties of the material.Comment: 11 pages including 9 figures. Submitted to Phys. Rev. B. Related publications can be found at http://www.fhi-berlin.mpg.de/th/paper.htm

Evidence for localization and 0.7 anomaly in hole quantum point contacts

Quantum point contacts implemented in p-type GaAs/AlGaAs heterostructures are investigated by low-temperature electrical conductance spectroscopy measurements. Besides one-dimensional conductance quantization in units of $2e^{2}/h$ a pronounced extra plateau is found at about $0.7(2e^{2}/h)$ which possesses the characteristic properties of the so-called "0.7 anomaly" known from experiments with n-type samples. The evolution of the 0.7 plateau in high perpendicular magnetic field reveals the existence of a quasi-localized state and supports the explanation of the 0.7 anomaly based on self-consistent charge localization. These observations are robust when lateral electrical fields are applied which shift the relative position of the electron wavefunction in the quantum point contact, testifying to the intrinsic nature of the underlying physics.Comment: 4.2 pages, 3 figure

Epitaxial Core-Shell Oxide Nanoparticles: First-Principles Evidence for Increased Activity and Stability of Rutile Catalysts for Acidic Oxygen Evolution

Using first-principles density-functional theory calculations combined with ab initio thermodynamics, we introduce a design protocol for RuO2-based core-shell catalysts which exhibit enhanced stability and activity under oxygen evolution reaction (OER) operating conditions. Due to their high activity and favorable stability in acidic electrolytes, Ir and Ru oxides are primary catalysts for the oxygen evolution reaction (OER) in proton-exchange membrane (PEM) electrolyzers. For a future large-scale application, core-shell nanoparticles are an appealing route to minimize the demand for these precious oxides. Here, we employ first-principles density-functional theory (DFT) and ab initio thermodynamics to assess the feasibility of encapsulating a cheap rutile-structured TiO2 core with coherent, monolayer-thin IrO2 or RuO2 films. Resulting from a strong directional dependence of adhesion and strain, a wetting tendency is only obtained for some low-index facets under typical gas-phase synthesis conditions. Thermodynamic stability in particular of lattice-matched RuO2 films is instead indicated for more oxidizing conditions. Intriguingly, the calculations also predict an enhanced activity and stability of such epitaxial RuO2/TiO2 core-shell particles under OER operation

Accuracy of first-principles lateral interactions: Oxygen at Pd(100)

We employ a first-principles lattice-gas Hamiltonian (LGH) approach to determine the lateral interactions between O atoms adsorbed on the Pd(100) surface. With these interactions, we obtain an ordering behavior at low coverage that is in quantitative agreement with experimental data. Uncertainties in the approach arise from the finite LGH expansion and from the approximate exchange-correlation (xc) functional underlying the employed density-functional theory energetics. We carefully scrutinize these uncertainties and conclude that they primarily affect the on-site energy, which rationalizes the agreement with the experimental critical temperatures for the order-disorder transition. We also investigate the validity of the frequently applied assumption that the ordering energies can be represented by a sum of pair terms. Restricting our LGH expansion to just pairwise lateral interactions, we find that this results in effective interactions which contain spurious contributions that are of equal size, if not larger than any of the uncertainties, e.g., due to the approximate xc functional

Heterogeneous Catalysis in Grammar School

The discovery of new catalytically active materials is one of the holy grails of computational chemistry as it has the potential to accelerate the adoption of renewable energy sources and reduce the energy consumption of chemical industry. Indeed, heterogeneous catalysis is essential for the production of synthetic fuels and many commodity chemicals. Consequently, novel solid catalysts with higher activity and selectivity, increased sustainability and longevity, or improved prospects for rejuvenation and cyclability are needed for a diverse range of processes. Unfortunately, computational catalyst discovery is a daunting task, among other reasons because it is often unclear whether a proposed material is stable or synthesizable. This perspective proposes a new approach to this challenge, namely the use of generative grammars. We outline how grammars can guide the search for stable catalysts in a large chemical space and sketch out several research directions that would make this technology applicable to real materials