The shortcomings of semi-local and hybrid functionals: what we can learn from surface science studies

A study of the adsorption of CO on late 4d and $5d$ transition metal (111) surfaces (Ru, Rh, Pd, Ag, Os, Ir, and Pt) considering atop and hollow site adsorption is presented. The applied functionals include the gradient corrected PBE and BLYP functional, and the corresponding hybrid Hartree-Fock density functionals HSE and B3LYP. We find that PBE based hybrid functionals (specifically HSE) yield, with the exception of Pt, the correct site order on all considered metals, but they also considerably overestimate the adsorption energies compared to experiment. On the other hand, the semi-local BLYP functional and the corresponding hybrid functional B3LYP yield very satisfactory adsorption energies and the correct adsorption site for all surfaces. We are thus faced with a Procrustean problem: the B3LYP and BLYP functionals seem to be the overall best choice for describing adsorption on metal surfaces, but they simultaneously fail to account well for the properties of the metal, vastly overestimating the equilibrium volume and underestimating the atomization energies. Setting out from these observations, general conclusions are drawn on the relative merits and drawbacks of various semi-local and hybrid functionals. The discussion includes a revised version of the PBE functional specifically optimized for bulk properties and surface energies (PBEsol), a revised version of the PBE functional specifically optimized to predict accurate adsorption energies (rPBE), as well as the aforementioned BLYP functional. We conclude that no semi-local functional is capable to describe all aspects properly, and including non-local exchange also only improves some, but worsens other properties.Comment: 12 pages, 6 figures; to be published in New Journal of Physic

The role of social interaction in farmers' climate adaptation choice

Adaptation to climate change might not always occur, with potentially\ud catastrophic results. Success depends on coordinated actions at both\ud governmental and individual levels (public and private adaptation). Even for a “wet” country like the Netherlands, climate change projections show that the frequency and severity of droughts are likely to increase. Freshwater is an important factor for agricultural production. A deficit causes damage to crop production and consequently to a loss of income. Adaptation is the key to decrease farmers’ vulnerability at the micro level and the sector’s vulnerability at the macro level. Individual adaptation decision-making is determined by the behavior of economic agents and social interaction among them. This can be best studied with agentbased modelling. Given the uncertainty about future weather conditions and the costs and effectiveness of adaptation strategies, a farmer in the model uses a cognitive process (or heuristic) to make adaptation decisions. In this process, he can rely on his experiences and on information from interactions within his social network. Interaction leads to the spread of information and knowledge that causes learning. Learning changes the conditions for individual adaptation decisionmaking. All these interactions cause emergent phenomena: the diffusion of adaptation strategies and a change of drought vulnerability of the agricultural sector. In this paper, we present a conceptual model and the first implementation of an agent-based model. The aim is to study the role of interaction in a farmer’s social network on adaptation decisions and on the diffusion of adaptation strategies\ud and vulnerability of the agricultural sector. Micro-level survey data will be used to parameterize agents’ behavioral and interaction rules at a later stage. This knowledge is necessary for the successful design of public adaptation strategies, since governmental adaptation actions need to be fine-tuned to private adaptation behavior

Dense and warm molecular gas in the envelopes and outflows of southern low-mass protostars

Observations of dense molecular gas lie at the basis of our understanding of the density and temperature structure of protostellar envelopes and molecular outflows. We aim to characterize the properties of the protostellar envelope, molecular outflow and surrounding cloud, through observations of high excitation molecular lines within a sample of 16 southern sources presumed to be embedded YSOs. Observations of submillimeter lines of CO, HCO+ and their isotopologues, both single spectra and small maps were taken with the FLASH and APEX-2a instruments mounted on APEX to trace the gas around the sources. The HARP-B instrument on the JCMT was used to map IRAS 15398-3359 in these lines. HCO+ mapping probes the presence of dense centrally condensed gas, a characteristic of protostellar envelopes. The rare isotopologues C18O and H13CO+ are also included to determine the optical depth, column density, and source velocity. The combination of multiple CO transitions, such as 3-2, 4-3 and 7-6, allows to constrain outflow properties, in particular the temperature. Archival submillimeter continuum data are used to determine envelope masses. Eleven of the sixteen sources have associated warm and/or dense quiescent as characteristic of protostellar envelopes, or an associated outflow. Using the strength and degree of concentration of the HCO+ 4-3 and CO 4-3 lines as a diagnostic, five sources classified as Class I based on their spectral energy distributions are found not to be embedded YSOs. The C18O 3-2 lines show that for none of the sources, foreground cloud layers are present. Strong molecular outflows are found around six sources, .. (continued in paper)Comment: Accepted by A&A, 13 figure

Cold trapped atoms detected with evanescent waves

We demonstrate the in situ detection of cold 87 Rb atoms near a dielectric surface using the absorption of a weak, resonant evanescent wave. We have used this technique in time of flight experiments determining the density of atoms falling on the surface. A quantitative understanding of the measured curve was obtained using a detailed calculation of the evanescent intensity distribution. We have also used it to detect atoms trapped near the surface in a standing-wave optical dipole potential. This trap was loaded by inelastic bouncing on a strong, repulsive evanescent potential. We estimate that we trap 1.5 x 10 4 atoms at a density 100 times higher than the falling atoms.Comment: 5 pages, 3 figure

Why is a noble metal catalytically active? The role of the O-Ag interaction in the function of silver as an oxidation catalyst

Extensive density-functional theory calculations, and taking into account temperature and pressure, affords a comprehensive picture of the behavior and interaction of oxygen and Ag(111), and provides valuable insight into the function of silver as an oxidation catalyst. The obtained phase-diagram reveals the most stable species present in a given environment and thus identifies (and excludes) possibly active oxygen species. In particular, for the conditions of ethylene epoxidation, a thin oxide-like structure is most stable, suggesting that such atomic O species are actuating the catalysis, in contrast to hitherto proposed molecular-like species.Comment: 4 pages including 3 figures, Related publications can be found at http://www.fhi-berlin.mpg.de/th/paper.htm

Pest species diversity enhances control of spider mites and whiteflies by a generalist phytoseiid predator

To test the hypothesis that pest species diversity enhances biological pest control with generalist predators, we studied the dynamics of three major pest species on greenhouse cucumber: Western flower thrips, Frankliniella occidentalis (Pergande), greenhouse whitefly, Trialeurodes vaporariorum (Westwood), and two-spotted spider mites, Tetranychus urticae Koch in combination with the predator species Amblyseius swirskii Athias-Henriot. When spider mites infested plants prior to predator release, predatory mites were not capable of controlling spider mite populations in the absence of other pest species. A laboratory experiment showed that predators were hindered by the webbing of spider mites. In a greenhouse experiment, spider mite leaf damage was lower in the presence of thrips and predators than in the presence of whiteflies and predators, but damage was lowest in the presence of thrips, whiteflies and predators. Whitefly control was also improved in the presence of thrips. The lower levels of spider mite leaf damage probably resulted from (1) a strong numerical response of the predator (up to 50 times higher densities) when a second and third pest species were present in addition to spider mites, and (2) from A. swirskii attacking mobile spider mite stages outside or near the edges of the spider mite webbing. Interactions of spider mites with thrips and whiteflies might also result in suppression of spider mites. However, when predators were released prior to spider mite infestations in the absence of other pest species, but with pollen as food for the predators, we found increased suppression of spider mites with increased numbers of predators released, confirming the role of predators in spider mite control. Thus, our study provides evidence that diversity of pest species can enhance biological control through increased predator densitie

Cosmological tensor perturbations in the Randall-Sundrum model: evolution in the near-brane limit

We discuss the evolution of cosmological tensor perturbations in the RSII model. In Gaussian normal coordinates the wave equation is non-separable, so we use the near-brane limit to perform the separation and study the evolution of perturbations. Massive excitations, which may also mix, decay outside the horizon which could lead to some novel cosmological signatures.Comment: 18 pages, 1 figur