Diffusion of Hydrogen in Pd Assisted by Inelastic Ballistic Hot Electrons

Sykes {\it et al.} [Proc. Natl. Acad. Sci. {\bf 102}, 17907 (2005)] have reported how electrons injected from a scanning tunneling microscope modify the diffusion rates of H buried beneath Pd(111). A key point in that experiment is the symmetry between positive and negative voltages for H extraction, which is difficult to explain in view of the large asymmetry in Pd between the electron and hole densities of states. Combining concepts from the theory of ballistic electron microscopy and electron-phonon scattering we show that H diffusion is driven by the $s$-band electrons only, which explains the observed symmetry.Comment: 5 pages and 4 figure

Diffusion of hydrogen interstitials in the near-surface region of Pd(111) under the influence of surface coverage and external static electric fields

Past scanning tunneling microscopy (STM) experiments of H manipulation on Pd(111), at low temperature, have shown that it is possible to induce diffusion of surface species as well as of those deeply buried under the surface. Several questions remain open regarding the role of subsurface site occupancies. In the present work, the interaction potential of H atoms with Pd(111) under various H coverage conditions is determined by means of density functional theory calculations in order to provide an answer to two of these questions: (i) whether subsurface sites are the final locations for the H impurities that attempt to emerge from bulk regions, and (ii) whether penetration of the surface is a competing route of on-surface diffusion during depletion of surface H on densely covered Pd(111). We find that a high H coverage has the effect of blocking resurfacing of H atoms travelling from below, which would otherwise reach the surface fcc sites, but it hardly alters deeper diffusion energy barriers. Penetration is unlikely and restricted to high occupancies of hcp hollows. In agreement with experiments, the Pd lattice expands vertically as a consequence of H atoms being blocked at subsurface sites, and surface H enhances this expansion. STM tip effects are included in the calculations self-consistently as an external static electric field. The main contribution to the induced surface electric dipoles originates from the Pd substrate polarisability. We find that the electric field has a non- negligible effect on the H-Pd potential in the vicinity of the topmost Pd atomic layer, yet typical STM intensities of 1-2 VÅ−1 are insufficient to invert the stabilities of the surface and subsurface equilibrium sites

Texture Extraction Techniques for the Classification of Vegetation Species in Hyperspectral Imagery: Bag of Words Approach Based on Superpixels

Texture information allows characterizing the regions of interest in a scene. It refers to the spatial organization of the fundamental microstructures in natural images. Texture extraction has been a challenging problem in the field of image processing for decades. In this paper, different techniques based on the classic Bag of Words (BoW) approach for solving the texture extraction problem in the case of hyperspectral images of the Earth surface are proposed. In all cases the texture extraction is performed inside regions of the scene called superpixels and the algorithms profit from the information available in all the bands of the image. The main contribution is the use of superpixel segmentation to obtain irregular patches from the images prior to texture extraction. Texture descriptors are extracted from each superpixel. Three schemes for texture extraction are proposed: codebook-based, descriptor-based, and spectral-enhanced descriptor-based. The first one is based on a codebook generator algorithm, while the other two include additional stages of keypoint detection and description. The evaluation is performed by analyzing the results of a supervised classification using Support Vector Machines (SVM), Random Forest (RF), and Extreme Learning Machines (ELM) after the texture extraction. The results show that the extraction of textures inside superpixels increases the accuracy of the obtained classification map. The proposed techniques are analyzed over different multi and hyperspectral datasets focusing on vegetation species identification. The best classification results for each image in terms of Overall Accuracy (OA) range from 81.07% to 93.77% for images taken at a river area in Galicia (Spain), and from 79.63% to 95.79% for a vast rural region in China with reasonable computation timesThis work was supported in part by the Civil Program UAVs Initiative, promoted by the Xunta de Galicia and developed in partnership with the Babcock Company to promote the use of unmanned technologies in civil services. We also have to acknowledge the support by Ministerio de Ciencia e Innovación, Government of Spain (grant number PID2019-104834GB-I00), and Consellería de Educación, Universidade e Formación Profesional (ED431C 2018/19, and accreditation 2019-2022 ED431G-2019/04). All are cofunded by the European Regional Development Fund (ERDF)S

Dynamics and morpho-sedimentary interactions in the lower mesotidal estuary of Villaviciosa (NW Spain) : A management proposal

The accumulation of sediment in the mouth of Villaviciosa estuary (NW Spain) is becoming an obstaclefor the safe navigation in this estuary. One sector of its outer inlet is characterised by a broad shoal linkedwith a longshore bar of a beach, whose erosion is causing the silting of this area. On this basis, this paperaims to describe the processes that occurred in the lower part of the estuary due to the anthropogenicactivities in the channel and inlet. For this purpose, several measurements were made in the watercolumn and in the sedimentary bottoms to characterise the processes that occur in this area. Based onthese results, a dynamic and morpho-sedimentary model was developed to examine the interactionsbetween the lower estuary and the exposed part of the confining barrier beach, which allows to establishthe evolutionary trends of sedimentary bottoms linked to the marina of El Puntal. Different managementmeasures are carried out to reduce the impact of the sediment accumulation on the navigability, such asperiodically dredging in the inlet of the estuary, and the subsequent dumping of the sediments in areasnear to the closure depth. Consequently, future retreat of narrow inlet and sandy shoal can be avoided,maintaining the sedimentary volume in the system

Finding the subtle balance between van der Waals interactions and hybridisation

We use density-functional theory (DFT) to analyse the interaction of trans- and cis-porphycene with Cu(111) and their interconversion by intramolecular H-transfer. This tautomerisation reaction is characterised by small values for the reaction energy and barrier, on the order of ∼0.1 eV, where the trans configuration is thermodynamically more stable upon adsorption according to the experiments [J. N. Ladenthin et al., ACS Nano 9, 7287–7295 (2015)]. To gain even a qualitatively correct description of this reaction at the DFT level, an accurate treatment of dispersion interactions and a careful choice of the exchange contribution are required in order to predict the subtle energetics. Analysis of the electronic structure shows that adsorption is contributed by a van der Waals (vdW) interaction, mainly responsible for stabilising the polyaromatic fragments, and by a significant charge redistribution localised between Cu and the unsaturated N atoms of the molecule central cavity. We find that different vdW functionals can produce qualitatively different electronic structures, while yielding small trans vs. cis energy differences. Unlike other functionals surveyed here, vdW-DF with PBE exchange satisfactorily reproduces not only the experimental energetics but also the scanning tunneling microscopy images. This gives us confidence that this functional achieves a reliable balance between the two mechanisms contributing to the adsorption of porphycene

The PointGroupNRG code for numerical renormalization group calculations with discrete point-group symmetries

The numerical renormalization group (NRG) has been widely used as a magnetic impurity solver since the pioneering works by Wilson. Over the past decades, a significant attention has been focused on the application of symmetries in order to reduce the computational cost of the calculations and to improve their accuracy. In particular, a notable progress has been made in implementing continuous symmetries such as $SO(3)$, useful for studying impurities in an isotropic medium, or $SU(N)$, which is applicable to a wide range of systems. In this work, we focus on the application of discrete point group symmetries, which are particularly relevant for impurity systems in metals where crystal field effects are important. With this aim, we have developed an original NRG code written in the Julia language, PointGroupNRG, where we have implemented crystal point-group symmetries for the Anderson impurity model, as well as the continuous spin and charge symmetries. Among other results, we demonstrate the advantage of our procedure by performing thermodynamic calculations for an impurity system with two orbitals of $E_g$ symmetry and two channels. We compare the results with those obtained for an approximate equivalent model with continuous orbital symmetry.Comment: 17 pages, 1 figur

Quantitative LEED analysis using a simultaneous optimisation algorithm

The performance of a combinatorial simultaneous optimisation algorithm (SO) is tested using experimental LEED I(E) data from Cu(100) and Fe$_{0.57}$Al$_{0.47}$(100) surfaces. SO optimises structures taking advantage of the experimental database at two levels: (i) conmensurate subsets of the database with the number of unknown parameters are chosen to find local solutions using Broyden's method and, (ii) these partial structural solutions are used to build a Markov chain over the whole database. This procedure is of global character, the same as simulated annealing or genetic algorithms methods, but displays a very competitive scaling law because after the first iteration candidates are not chosen by a blind/random pick; they are already solutions to the problem with a restricted experimental database.Financed by CYCIT (MAT-2005-3866) and MEC (CONSOLIDER NANOSELEC-26400