The local structure of SO2 and SO3 on Ni(1 1 1): a scanned-energy mode photoelectron diffraction study

O 1s and S 2p scanned-energy mode photoelectron diffraction (PhD) data, combined with multiple-scattering simulations, have been used to determine the local adsorption geometry of the SO2 and SO3 species on a Ni(1 1 1) surface. For SO2, the application of reasonable constraints on the molecular conformation used in the simulations leads to the conclusion that the molecule is centred over hollow sites on the surface, with the molecular plane essentially parallel to the surface, and with both S and O atoms offset from atop sites by almost the same distance of 0.65 Å. For SO3, the results are consistent with earlier work which concluded that surface bonding is through the O atoms, with the S atom higher above the surface and the molecular symmetry axis almost perpendicular to the surface. Based on the O 1s PhD data alone, three local adsorption geometries are comparably acceptable, but only one of these is consistent with the results of an earlier normal-incidence X-ray standing wave (NIXSW) study. This optimised structural model differs somewhat from that originally proposed in the NIXSW investigation

Structure determination of PF3 adsorption on Cu(100) using X-ray standing waves

The local structure of the Cu(100)c(4x2)-PF3 adsorption phase has been investigated through the use of normal-incidence X-ray standing waves (NIXSW), monitored by P 1s and F 1s photoemission, together with P K-edge near-edge X-ray absorption fine structure (NEXAFS). NEXAFS shows the molecule to be oriented with its C3v symmetry axis essentially perpendicular to the surface, while the P NIXSW data show the molecule to be adsorbed in atop sites 2.37±0.04 Å above the surface, this distance corresponding to the Cu-P nearest-neighbour distance in the absence of any surface relaxation. F NIXSW indicates a surprisingly small height difference of the P and F atoms above the surface 0.44±0.06 Å, compared with the value expected for an undistorted gas-phase geometry of 0.77 Å, implying significant increases in the F-P-F bond angles. In addition, however, the F NIXSW data indicate that the molecules have a well-defined azimuthal orientation with a molecular mirror plane aligned in a substrate mirror plane, and with a small (5-10°) tilt of the molecule in this plane such that the two symmetrically-equivalent F atoms in each molecule are tilted down towards the surface

The local adsorption structure of methylthiolate and butylthiolate on Au(1 1 1): a photoemission core-level shift investigation

Measurements of the core-level shifts in Au 4f photoemission spectra from Au(1 1 1) at different coverages of methylthiolate and butylthiolate are reported. Adsorption leads to two components in addition to that from the bulk, one at lower photoelectron binding energy attributed to surface atoms not bonded to thiolate species, while the second component has a higher binding energy and is attributed to Au atoms bonded to the surface thiolate. The relative intensities of these surface components for the saturation coverage (mainly (√3 × √3)R30°) phases are discussed in terms of different local adsorption sites in a well-ordered surface, and favour adsorption of the thiolate species atop Au adatoms. Alternative interpretations that might be consistent with an Au-adatom-dithiolate model are discussed, particularly in the context of the possible influence of reduced coverage associated with a disordered surface. Marked differences from previously-reported results for longer-chain alkylthiolate layers are highlighted

The (2√3×3)rect. phase of alkylthiolate self-assembled monolayers on Au(111): a symmetry-constrained structural solution

Low-energy electron-diffraction (LEED) patterns of the Au(111)(2√3×3)rect.-butylthiolate surface phase (a structure also seen in longer alkane chain thiolate self-assembled monolayers) show missing diffracted beams characteristic of glide symmetry, but do not show the larger set of missing beams found in surface x-ray diffraction (SXRD). The difference can be attributed to the greatly enhanced role of multiple scattering in LEED, but the combination of symmetry constraints placed on possible structural models by the observed SXRD and LEED beam extinctions greatly reduces the number of possible structural models. Only three such models are identified, one of which is clearly incompatible with other published experimental data. The relative merits of the remaining models, both involving Au adatom-thiolate moieties, are discussed in the light of the results of previous experimental studies

P4DNS: In-Network DNS

In network computing offers an appealing scalability trajectory for network services, as application performance scales with network devices. Despite its potential, in-network computing may not be suitable for all applications, both due to paradigm assumptions and network-device limitations. As the users' demands from the Internet keep growing, any limitations on the scalability of network services such as DNS limits the scalability of end-to-end experience. In this paper we present P4DNS, an in-network DNS solution, exploring the span and limitations of implementing a realistic network service within a network device. P4DNS is a high performance DNS server, implemented in P4->NetFPGA and providing performance improvement compared with software-based solutions. We discuss the limitations of implementing in-network services using today's paradigms and the trade-offs between data and control planesLeverhulme Trust Isaac Newton Trus

Measuring Burstiness in Data Center Applications

Buffer sizing is a tricky task --- it depends on a large number of variables, ranging from congestion control to traffic engineering. Still, the most unpredictable contributors are the workloads running in the network. The link utilization and burstiness of these workloads dictate the buffer depth needed by a switch. But what is a burst? Do traditional definitions still apply in the age in which switches transfer terabits of data and billions of packets every second? Unless we assess bursts correctly, we are unlikely to size buffers appropriately. In this work, we present a measurement-led evaluation of the burstiness of different data center applications. We address the question of ``what is a burst?'' and assert that common techniques cannot answer this question in modern data centers. We quantify the change in burstiness of the studied applications across multiple vectors, including latency and network perspective, and generalize our results to the common case. Our observations can inform future buffer sizing efforts and guide switch configurations. Our dataset is openly available for the benefit of the community.Leverhulme Trust Isaac Newton Trus

The local adsorption site of methylthiolate on Au(1 1 1): Bridge or atop?

Measurements of the local adsorption geometry of the S head-group atom in the Au(1 1 1)(√3 × √3)R30°–CH3S surface have been made using normal incidence X-ray standing waves (NIXSW) and S 1s scanned-energy mode photoelectron diffraction on the same surface preparations. The results confirm that the local adsorption site is atop an Au atom in a bulk-continuation site with a S–Au bondlength of 2.42 ± 0.02 Å, and that there can be no significant fraction of coadsorbed bridging species as recently proposed in a combined molecular dynamics/experimental study by Mazzarello et al. [R. Mazzarello, A. Cossaro, A. Verdini, R. Rousseau, L. Casalis, M.F. Danisman, L. Floreano, S. Scandolo, A. Morgante, G. Scoles, Phys. Rev. Lett. 98 (2007) 016102]. The results do not, however, clearly distinguish the different local reconstruction (adatom) models proposed for this surface

Local methylthiolate adsorption geometry on Au(111) from photoemission core-level shifts

The local adsorption structure of methylthiolate in the ordered Au(111)-(√3×√3)R30° phase has been investigated using core-level-shift measurements of the surface and bulk components of the Au 4f7/2 photoelectron binding energy. The amplitude ratio of the core-level-shift components associated with surface Au atoms that are, and are not, bonded to the thiolate is found to be compatible only with the previously proposed Au-adatom-monothiolate moiety in which the thiolate is bonded atop Au adatoms in hollow sites, and not on an unreconstructed surface, or in Au-adatom-dithiolate species

The local adsorption geometry of benzenethiolate on Cu(1 0 0)

The local adsorption geometry of benzenethiolate in the ordered c(2 × 6) phase on Cu(1 0 0) has been investigated by a combination of S K-edge near-edge X-ray absorption fine structure (NEXAFS), normal incidence X-ray standing waves (NIXSW) and S 1s scanned-energy mode photoelectron diffraction (PhD). NEXAFS and PhD show that the molecular plane is tilted from the surface normal by 20 ± 15°, while NIXSW clearly identifies the S head-group as occupying the four-fold coordinated hollow sites. PhD shows the S atoms lies 1.34 ± 0.04 Å above the outermost Cu atomic layer, leading to a Cu–S bondlength of 2.25 ± 0.02 Å. The combination of the PhD and NIXSW results shows the Cu surface layer has an outward relaxation of 0.15 ± 0.06 Å. Possible origins for this large adsorbate-induced relaxation are discussed