2,754 research outputs found
A photoelectron diffraction investigation of vanadyl phthalocyanine on Au(1 1 1)
Scanned-energy mode photoelectron diffraction using the O 1s and V 2p emission perpendicular to the surface has been used to investigate the orientation and internal conformation of vanadyl phthalocyanine (VOPc) adsorbed on Au(1 1 1). The results confirm earlier indications from scanning tunnelling microscopy that the Vdouble bond; length as m-dashO vanadyl bond points out of, and not into, the surface. The Vdouble bond; length as m-dashO bondlength is 1.60 ± 0.04 Å, not significantly different from its value in bulk crystalline VOPc. However, the V atom in the adsorbed molecule is almost coplanar with the surrounding N atoms and is thus pulled down into the approximately planar region defined by the N and C atoms by 0.52 (+0.14/−0.10) Å, relative to its location in crystalline VOPc. This change must be attributed to the bonding interaction between the molecule and the underlying metal surface
The structure of the Au(111)/methylthiolate interface : new insights from near-edge X-ray absorption spectroscopy and X-ray standing waves
The local structure of the Au(111)([square root of]3×[square root of]3)R30°-methylthiolate surface phase has been investigated by S K-edge near-edge s-ray absorption fine structure (NEXAFS) both experimentally and theoretically and by experimental normal-incidence x-ray standing waves (NIXSW) at both the C and S atomic sites. NEXAFS shows not only excitation into the intramolecular sigma* S–C resonance but also into a sigma* S–Au orbital perpendicular to the surface, clearly identifying the local S headgroup site as atop a Au atom. Simulations show that it is not possible, however, to distinguish between the two possible adatom reconstruction models; a single thiolate species atop a hollow-site Au adatom or a dithiolate moiety comprising two thiolate species bonded to a bridge-bonded Au adatom. Within this dithiolate moiety a second sigma* S–Au orbital that lies near parallel to the surface has a higher energy that overlaps that of the sigma* S–C resonance. The new NIXSW data show the S–C bond to be tilted by 61° relative to the surface normal, with a preferred azimuthal orientation in , corresponding to the intermolecular nearest-neighbor directions. This azimuthal orientation is consistent with the thiolate being atop a hollow-site Au adatom, but not consistent with the originally proposed Au-adatom-dithiolate moiety. However, internal conformational changes within this species could, perhaps, render this model also consistent with the experimental data
Adsorption structure of glycine on TiO2(1 1 0): a photoelectron diffraction determination
High-resolution core-level photoemission and scanned-energy mode photoelectron diffraction (PhD) of the O 1s and N 1s states have been used to investigate the interaction of glycine with the rutile TiO2(1 1 0) surface. Whilst there is clear evidence for the presence of the zwitterion View the MathML sourceCH2COO− with multilayer deposition, at low coverage only the deprotonated glycinate species, NH2CH2COO is present. Multiple-scattering simulations of the O 1s PhD data show the glycinate is bonded to the surface through the two carboxylate O atoms which occupy near-atop sites above the five-fold-coordinated surface Ti atoms, with a Ti–O bondlength of 2.12 ± 0.06 Å. Atomic hydrogen arising from the deprotonation is coadsorbed to form hydroxyl species at the bridging oxygen sites with an associated Ti–O bondlength of 2.01 ± 0.03 Å. Absence of any significant PhD modulations of the N 1s emission is consistent with the amino N atom not being involved in the surface bonding, unlike the case of glycinate on Cu(1 1 0) and Cu(1 0 0)
Direct calculation of the hard-sphere crystal/melt interfacial free energy
We present a direct calculation by molecular-dynamics computer simulation of
the crystal/melt interfacial free energy, , for a system of hard
spheres of diameter . The calculation is performed by thermodynamic
integration along a reversible path defined by cleaving, using specially
constructed movable hard-sphere walls, separate bulk crystal and fluid systems,
which are then merged to form an interface. We find the interfacial free energy
to be slightly anisotropic with = 0.62, 0.64 and
0.58 for the (100), (110) and (111) fcc crystal/fluid
interfaces, respectively. These values are consistent with earlier density
functional calculations and recent experiments measuring the crystal nucleation
rates from colloidal fluids of polystyrene spheres that have been interpreted
[Marr and Gast, Langmuir {\bf 10}, 1348 (1994)] to give an estimate of
for the hard-sphere system of , slightly lower
than the directly determined value reported here.Comment: 4 pages, 4 figures, submitted to Physical Review Letter
A Multi-scale Approach for Simulations of Kelvin Probe Force Microscopy with Atomic Resolution
The distance dependence and atomic-scale contrast observed in nominal contact
potential difference (CPD) signals recorded by KPFM on surfaces of insulating
and semiconducting samples, have stimulated theoretical attempts to explain
such effects. We attack this problem in two steps. First, the electrostatics of
the macroscopic tip-cantilever-sample system is treated by a finite-difference
method on an adjustable nonuniform mesh. Then the resulting electric field
under the tip apex is inserted into a series of atomistic wavelet-based density
functional theory (DFT) calculations. Results are shown for a realistic neutral
but reactive silicon nano-scale tip interacting with a NaCl(001) sample.
Bias-dependent forces and resulting atomic displacements are computed to within
an unprecedented accuracy. Theoretical expressions for amplitude modulation
(AM) and frequency modulation (FM) KPFM signals and for the corresponding local
contact potential differences (LCPD) are obtained by combining the macroscopic
and atomistic contributions to the electrostatic force component generated at
the voltage modulation frequency, and evaluated for several tip oscillation
amplitudes A up to 10 nm. Being essentially constant over a few Volts, the
slope of atomistic force versus bias is the basic quantity which determines
variations of the atomic-scale LCPD contrast. Already above A = 0.1 nm, the
LCPD contrasts in both modes exhibit almost the same spatial dependence as the
slope. In the AM mode, this contrast is approximately proportional to
, but remains much weaker than the contrast in the FM mode, which
drops somewhat faster as A is increased. These trends are a consequence of the
macroscopic contributions to the KPFM signal, which are stronger in the AM-mode
and especially important if the sample is an insulator even at sub-nanometer
separations where atomic-scale contrast appears.Comment: 19 pages, 13 figure
The neural correlates of emotion regulation by implementation intentions
Several studies have investigated the neural basis of effortful emotion regulation (ER) but the neural basis of automatic ER has been less comprehensively explored. The present study investigated the neural basis of automatic ER supported by ‘implementation intentions’. 40 healthy participants underwent fMRI while viewing emotion-eliciting images and used either a previously-taught effortful ER strategy, in the form of a goal intention (e.g., try to take a detached perspective), or a more automatic ER strategy, in the form of an implementation intention (e.g., “If I see something disgusting, then I will think these are just pixels on the screen!”), to regulate their emotional response. Whereas goal intention ER strategies were associated with activation of brain areas previously reported to be involved in effortful ER (including dorsolateral prefrontal cortex), ER strategies based on an implementation intention strategy were associated with activation of right inferior frontal gyrus and ventro-parietal cortex, which may reflect the attentional control processes automatically captured by the cue for action contained within the implementation intention. Goal intentions were also associated with less effective modulation of left amygdala, supporting the increased efficacy of ER under implementation intention instructions, which showed coupling of orbitofrontal cortex and amygdala. The findings support previous behavioural studies in suggesting that forming an implementation intention enables people to enact goal-directed responses with less effort and more efficiency
Quantitative adsorbate structure determination under catalytic reaction conditions
Current methods allow quantitative local structure determination of adsorbate geometries on surfaces in ultrahigh vacuum (UHV) but are incompatible with the higher pressures required for a steady-state catalytic reactions. Here we show that photoelectron diffraction can be used to determine the structure of the methoxy and formate reaction intermediates during the steady-state oxidation of methanol over Cu(110) by taking advantage of recent instrumental developments to allow near-ambient pressure x-ray photoelectron spectroscopy. The local methoxy site differs from that under static UHV conditions, attributed to the increased surface mobility and dynamic nature of the surface under reaction conditions
Bin Packing Problem with uncertainty on item availability: an application to Capacity Planning in Logistics
Most modern companies are part of international economic networks, where goods are produced under different strategies, then transported over long distances and stored for variable periods of time at different locations along the considered network. These activities are often performed by first consolidating goods in appropriate bins, which are then stored at warehouses and shipped using multiple vehicles through various transportation modes. Companies thus face the problem of planning for sufficient capacity, e.g., negotiating it with third party logistic firms (3PLs) that specify both the capacity to be used and the logistical services to be performed. Given the time lag that usually exists between the capacity-planning decisions and the operational decisions that define how the planned capacity is used, the common assumption that all information concerning the parameters of the model is known is unlikely to be observed. We therefore propose a new stochastic problem, named the Variable Cost and Size Bin Packing Problem with Stochastic Items. The problem considers a company making a tactical capacity plan by choosing a set of appropriate bins, which are defined according to their specific volume and fixed cost. Bins included in the capacity plan are chosen in advance without the exact knowledge of what items will be available for the dispatching. When, during the operational phase, the planned capacity is not sufficient, extra capacity must be purchased. An extensive experimental plan is used to analyze the impact that diversity in instance structure has on the capacity planning and the effect of considering different levels of variability and correlation of the stochastic parameters related to items
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