Delta Self-Consistent Field as a method to obtain potential energy surfaces of excited molecules on surfaces

We present a modification of the $\Delta$SCF 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 $\Delta$SCF approximation is a density functional method closely resembling standard density functional theory (DFT), the only difference being that in $\Delta$SCF one or more electrons are placed in higher lying Kohn-Sham orbitals, instead of placing all electrons in the lowest possible orbitals as one does when calculating the ground state energy within standard DFT. We extend the $\Delta$SCF method by allowing excited electrons to occupy orbitals which are linear combinations of Kohn-Sham orbitals. With this extra freedom it is possible to place charge locally on adsorbed molecules in the calculations, such that resonance energies can be estimated. The method is applied to N$_2$, CO and NO adsorbed on different metallic surfaces and compared to ordinary $\Delta$SCF without our modification, spatially constrained DFT and inverse-photoemission spectroscopy (IPES) measurements. This comparison shows that the modified $\Delta$SCF method gives results in close agreement with experiment, significantly closer than the comparable methods. For N$_2$ adsorbed on ruthenium (0001) we map out a 2-dimensional part of the potential energy surfaces in the ground state and the 2$\pi$-resonance. Finally we compare the $\Delta$SCF approach on gas-phase N$_2$ and CO, to higher accuracy methods. Excitation energies are approximated with accuracy close to that of time-dependent density functional theory, and we see very good agreement in the minimum shift of the potential energy surfaces in the excited state compared to the ground state.Comment: 11 pages, 7 figure

Copper flows in buildings, infrastructure and mobiles: a dynamic model and its application to Switzerland

During the last century, the consumption of materials for human needs increased by several orders of magnitude, even for non-renewable materials such as metals. Some data on annual consumption (input) and recycling/waste (output) can often be found in the federal statistics, but a clear picture of the main flows is missing. A dynamic material flow model is developed for the example of copper in Switzerland in order to simulate the relevant copper flows and stocks over the last 150years. The model is calibrated using data from statistical and published sources as well as from interviews and measurements. A simulation of the current state (2000) is compared with data from other studies. The results show that Swiss consumption and losses are both high, at a level of about 8 and 2kg/(capyear), respectively, or about three times higher than the world average. The model gives an understanding of the flows and stocks and their interdependencies as a function of time. This is crucial for materials whose consumption dynamics are characterised by long lifetimes and hence for relating the current output to the input of the whole past. The model allows a comprehensive discussion of possible measures to reduce resource use and losses to the environment. While increasing the recycling reduces losses to landfill, only copper substitution can reduce the different losses to the environment, although with a time delay of the order of a lifetim

The local electronic structure of alpha-Li3N

New theoretical and experimental investigation of the occupied and unoccupied local electronic density of states (DOS) are reported for alpha-Li3N. Band structure and density functional theory calculations confirm the absence of covalent bonding character. However, real-space full-multiple-scattering (RSFMS) calculations of the occupied local DOS finds less extreme nominal valences than have previously been proposed. Nonresonant inelastic x-ray scattering (NRIXS), RSFMS calculations, and calculations based on the Bethe-Salpeter equation are used to characterize the unoccupied electronic final states local to both the Li and N sites. There is good agreement between experiment and theory. Throughout the Li 1s near-edge region, both experiment and theory find strong similarities in the s- and p-type components of the unoccupied local final density of states projected onto an orbital angular momentum basis (l-DOS). An unexpected, significant correspondence exists between the near-edge spectra for the Li 1s and N 1s initial states. We argue that both spectra are sampling essentially the same final density of states due to the combination of long core-hole lifetimes, long photoelectron lifetimes, and the fact that orbital angular momentum is the same for all relevant initial states. Such considerations may be generically applicable for low atomic number compounds.Comment: 34 pages, 7 figures, 1 tabl

Connected component identification and cluster update on GPU

Cluster identification tasks occur in a multitude of contexts in physics and engineering such as, for instance, cluster algorithms for simulating spin models, percolation simulations, segmentation problems in image processing, or network analysis. While it has been shown that graphics processing units (GPUs) can result in speedups of two to three orders of magnitude as compared to serial codes on CPUs for the case of local and thus naturally parallelized problems such as single-spin flip update simulations of spin models, the situation is considerably more complicated for the non-local problem of cluster or connected component identification. I discuss the suitability of different approaches of parallelization of cluster labeling and cluster update algorithms for calculations on GPU and compare to the performance of serial implementations.Comment: 15 pages, 14 figures, one table, submitted to PR

Cortical circuit alterations precede motor impairments in Huntington's disease mice

Huntington's disease (HD) is a devastating hereditary movement disorder, characterized by degeneration of neurons in the striatum and cortex. Studies in human patients and mouse HD models suggest that disturbances of neuronal function in the neocortex play an important role in disease onset and progression. However, the precise nature and time course of cortical alterations in HD have remained elusive. Here, we use chronic in vivo two-photon calcium imaging to longitudinally monitor the activity of identified single neurons in layer 2/3 of the primary motor cortex in awake, behaving R6/2 transgenic HD mice and wildtype littermates. R6/2 mice show age-dependent changes in cortical network function, with an increase in activity that affects a large fraction of cells and occurs rather abruptly within one week, preceeding the onset of motor defects. Furthermore, quantitative proteomics demonstrate a pronounced downregulation of synaptic proteins in the cortex, and histological analyses in R6/2 mice and human HD autopsy cases reveal a reduction in perisomatic inhibitory synaptic contacts on layer 2/3 pyramidal cells. Taken together, our study provides a time-resolved description of cortical network dysfunction in behaving HD mice and points to disturbed excitation/inhibition balance as an important pathomechanism in HD

Further Characterization of Dopamine Release by Permeabilized PC 12 Cells

Rat pheochromocytoma cells (PC 12) permeabilized with staphylococcal α-toxin release [3H]dopamine after addition of micromolar Ca2+. This does not require additional Mg2+-ATP (in contrast to bovine adrenal medullary chromaffin cells). We also observed Ca2+-dependent [3H]-dopamine release from digitonin-permeabilized PC 12 cells. Permeabilization with α-toxin or digitonin and stimulation of the cells were done consecutively to wash out endogenous Mg2+-ATP. During permeabilization, ATP was removed effectively from the cytoplasm by both agents but the cells released [3H]dopamine in response to micromolar Ca2+ alone. Replacement by chloride of glutamate, which could sustain mitochondrial ATP production in permeabilized cells, does not significantly alter catecholamine release induced by Ca2+. However, Mg2+ without ATP augments the Ca2+-induced release. The release was unaltered by thiol-, hydroxyl-, or calmodulin-interfering substances. Thus Mg2+-ATP, calmodulin, or proteins containing -SH or -OH groups are not necessary for exocytosis in permeabilized PC 12 cells

Rapid leukocyte migration by integrin-independent flowing and squeezing

All metazoan cells carry transmembrane receptors of the integrin family, which couple the contractile force of the actomyosin cytoskeleton to the extracellular environment. In agreement with this principle, rapidly migrating leukocytes use integrin-mediated adhesion when moving over two-dimensional surfaces. As migration on two-dimensional substrates naturally overemphasizes the role of adhesion, the contribution of integrins during three-dimensional movement of leukocytes within tissues has remained controversial. We studied the interplay between adhesive, contractile and protrusive forces during interstitial leukocyte chemotaxis in vivo and in vitro. We ablated all integrin heterodimers from murine leukocytes, and show here that functional integrins do not contribute to migration in three-dimensional environments. Instead, these cells migrate by the sole force of actin-network expansion, which promotes protrusive flowing of the leading edge. Myosin II-dependent contraction is only required on passage through narrow gaps, where a squeezing contraction of the trailing edge propels the rigid nucleus

Identifying structural and energetic trends in isovalent core-shell nanoalloys as a function of composition and size mismatch

Producción CientíficaWe locate the putative global minimum structures of NaxCs(55 − x) and LixCs(55 − x) nanoalloys through combined empirical potential and density functional theory calculations, and compare them to the structures of 55-atom Li-Na and Na-K nanoalloys obtained in a recent paper [A. Aguado and J. M. López, J. Chem. Phys. 133, 094302 (2010)10.1063/1.3479396]. Alkali nanoalloys are representative of isovalent metallic mixtures with a strong tendency towards core-shell segregation, and span a wide range of size mismatches. By comparing the four systems, we analyse how the size mismatch and composition affect the structures and relative stabilities of these mixtures, and identify useful generic trends. The Na-K system is found to possess a nearly optimal size mismatch for the formation of poly-icosahedral (pIh) structures with little strain. In systems with a larger size mismatch (Na-Cs and Li-Cs), frustration of the pIh packing induces for some compositions a reconstruction of the core, which adopts instead a decahedral packing. When the size mismatch is smaller than optimal (Li-Na), frustration leads to a partial amorphization of the structures. The excess energies are negative for all systems except for a few compositions, demonstrating that the four mixtures are reactive. Moreover, we find that Li-Cs and Li-Na mixtures are more reactive (i.e., they have more negative excess energies) than Na-K and Na-Cs mixtures, so the stability trends when comparing the different materials are exactly opposite to the trends observed in the bulk limit: the strongly non-reactive Li-alkali bulk mixtures become the most reactive ones at the nanoscale. For each material, we identify the magic composition xm which minimizes the excess energy. xm is found to increase with the size mismatch due to steric crowding effects, and for LixCs(55 − x) the most stable cluster has almost equiatomic composition. We advance a simple geometric packing rule that suffices to systematize all the observed trends in systems with large size mismatch (Na-K, Na-Cs, and Li-Cs). As the size mismatch is reduced, however, electron shell effects become more and more important and contribute significantly to the stability of the Li-Na system