Ultrathin oxides: bulk-oxide-like model surfaces or unique films?

To better understand the electronic and chemical properties of wide-gap oxide surfaces at the atomic scale, experimental work has focused on epitaxial films on metal substrates. Recent findings show that these films are considerably thinner than previously thought. This raises doubts about the transferability of the results to surface properties of thicker films and bulk crystals. By means of density-functional theory and approximate GW corrections for the electronic spectra we demonstrate for three characteristic wide-gap oxides (silica, alumina, and hafnia) the influence of the substrate and highlight critical differences between the ultrathin films and surfaces of bulk materials. Our results imply that monolayer-thin oxide films have rather unique properties.Comment: 5 pages, 3 figures, accepted by PR

Large-scale surface reconstruction energetics of Pt(100) and Au(100) by all-electron DFT

The low-index surfaces of Au and Pt all tend to reconstruct, a fact that is of key importance in many nanostructure, catalytic, and electrochemical applications. Remarkably, some significant questions regarding their structural energies remain even today, in particular for the large-scale quasihexagonal reconstructed (100) surfaces: Rather dissimilar reconstruction energies for Au and Pt in available experiments, and experiment and theory do not match for Pt. We here show by all-electron density-functional theory that only large enough "(5 x N)" approximant supercells capture the qualitative reconstruction energy trend between Au(100) and Pt(100), in contrast to what is often done in the theoretical literature. Their magnitudes are then in fact similar, and closer to the measured value for Pt(100); our calculations achieve excellent agreement with known geometric characteristics and provide direct evidence for the electronic reconstruction driving force.Comment: updated version - also includes EPAPS information as auxiliary file; related publications can be found at http://www.fhi-berlin.mpg.de/th/th.htm

Multiscale approach to the electronic structure of doped semiconductor surfaces

The inclusion of the global effects of semiconductor doping poses a unique challenge for first-principles simulations, because the typically low concentration of dopants renders an explicit treatment intractable. Furthermore, the width of the space-charge region (SCR) at charged surfaces often exceeds realistic supercell dimensions. Here, we present a multiscale technique that fully addresses these difficulties. It is based on the introduction of a charged sheet, mimicking the SCR-related field, along with free charge which mimics the bulk charge reservoir, such that the system is neutral overall. These augment a slab comprising “pseudoatoms” possessing a fractional nuclear charge matching the bulk doping concentration. Self-consistency is reached by imposing charge conservation and Fermi level equilibration between the bulk, treated semiclassically, and the electronic states of the slab, which are treated quantum-mechanically. The method, called CREST—the charge-reservoir electrostatic sheet technique—can be used with standard electronic structure codes. We validate CREST using a simple tight-binding model, which allows for comparison of its results with calculations encompassing the full SCR explicitly. Specifically, we show that CREST successfully predicts scenarios spanning the range from no to full Fermi level pinning. We then employ it with density functional theory, obtaining insight into the doping dependence of the electronic structures of the metallic “clean-cleaved” Si(111) surface and its semiconducting (2×1) reconstructions

Image states in metal clusters

The existence of image states in small clusters is shown, using a quantum-mechanical many-body approach. We present image state energies and wave functions for spherical jellium clusters up to 186 atoms, calculated in the GW approximation, where G is the Green's function and W is the dynamically screened Coulomb interaction, which by construction contains the dynamic long-range correlation effects that give rise to image effects. In addition, we find that image states are also subject to quantum confinement. To extrapolate our investigations to clusters in the mesoscopic size range, we propose a semiclassical model potential, which we test against our full GW results

Defect Formation Energies without the Band-Gap Problem: Combining DFT and GW for the Silicon Self-Interstitial

We present an improved method to calculate defect formation energies that overcomes the band-gap problem of Kohn-Sham density-functional theory (DFT) and reduces the self-interaction error of the local-density approximation (LDA) to DFT. We demonstrate for the silicon self-interstitial that combining LDA with quasiparticle energy calculations in the G0W0 approach increases the defect formation energy of the neutral charge state by ~1.1 eV, which is in good agreement with diffusion Monte Carlo calculations (E. R. Batista et al. Phys. Rev. B 74, 121102(R) (2006), W.-K. Leung et al. Phys. Rev. Lett. 83, 2351 (1999)). Moreover, the G0W0-corrected charge transition levels agree well with recent measurements.Comment: 4 pages including 3 figures; related publications can be found at http://www.fhi-berlin.mpg.de/th/th.htm

Ground-based GNSS for climate research: review and perspectives

In climate research, the role of water vapour can hardly be overestimated. Water vapour is the most important natural greenhouse gas and is responsible for the largest known feedback mechanism for amplifying climate change. It also strongly influences atmospheric dynamics and the hydrologic cycle through surface evaporation, latent heat transport and diabatic heating, and is, in particular, a source of clouds and precipitation.Atmospheric water vapour is highly variable, both in space and in time. Therefore, measuring it remains a demanding and challenging task. The Zenith Total Delay (ZTD) estimated from GNSS observations, provided at a temporal resolution of minutes and under all weather conditions, can be converted to Integrated Water Vapour (IWV), if additional meteorological variables are available. Inconsistencies introduced into long-term time series from improved GNSS processing algorithms, instrumental, and environmental changes at GNSS stations make climate trend analyses challenging. Ongoing re-processing efforts using state-of-the-art models aim at providing consistent time series of tropospheric data, using 24+ years of GNSS observations from global and regional networks. GNSS is reaching the “maturity age” of 30 years when climate normal of ZTD/IWV (and horizontal gradients) can be derived. Being not assimilated in numerical weather prediction model reanalyses, GNSS products can also be used as independent datasets to validate climate model outputs (ZTD/IWV). However, what is the actual use of GNSS ZTDs in climate monitoring? What are the advantages of using GNSS ZTDs for climate monitoring? In addition, what would be the best ZTD time series to serve the climate community?The presentation will provide a review of the progress made in and the status of using GNSS tropospheric datasets for climate research, highlighting the challenges and pitfalls, and outlining the major remaining steps ahead. We will show examples demonstrating the benefits for climate monitoring brought by using GNSS ZTD and/or IWV datasets in complement to other observations.This contribution is related to the activities of JWG C.2: Quality control methods for climate applications of geodetic tropospheric parameters, https://iccc.iag-aig.org/joint-work-groups/216, of the IAG Inter-Commission Committee on "Geodesy for Climate Research" (ICCC)

Covariant Formulation of Field Theories associated with p-Branes

We discuss the covariant formulation of local field theories described by the Companion Lagrangian associated with p-branes. The covariantisation is shown to be useful for clarifying the geometrical meaning of the field equations and also their relation to the Hamilton-Jacobi formulation of the standard Dirac-Born-Infeld theory.Comment: 12 pages, Late

A Microfluidic Device for the Investigation of Rapid Gold Nanoparticle Formation in Continuous Turbulent Flow

A new setup with an integrated microfluidic chip with small dead time, high time resolution and compatibility with in situ X-ray absorption (XAS) measurements is presented. It can also be combined with a free liquid jet. By using the microfluidic chip the short reaction times from 2 to 20 milliseconds can be observed, beyond that an external cyclone mixer for extended observation times was applied. The reduction of gold ions with tetrakis(hydroxy-methyl)phosphonium (THPC) has been investigated in the microfluidic setup to monitor this reaction yielding small gold nanoparticles, requiring preferentially a free liquid jet