The exclusive use of integer-order spots for LEED-IV structure analysis of adsorption systems: p(2×2)-O on Ni{111}

Two different ways of performing low-energy electron diffraction (LEED) structure determinations for the p(2 x 2) structure of oxygen on Ni {111} are compared: a conventional LEED-IV structure analysis using integer and fractional-order IV-curves collected at normal incidence and an analysis using only integer-order IV-curves collected at three different angles of incidence. A clear discrimination between different adsorption sites can be achieved by the latter approach as well as the first and the best fit structures of both analyses are within each other's error bars (all less than 0.1 angstrom). The conventional analysis is more sensitive to the adsorbate coordinates and lateral parameters of the substrate atoms whereas the integer-order-based analysis is more sensitive to the vertical coordinates of substrate atoms. Adsorbate-related contributions to the intensities of integer-order diffraction spots are independent of the state of long-range order in the adsorbate layer. These results show, therefore, that for lattice-gas disordered adsorbate layers, for which only integer-order spots are observed, similar accuracy and reliability can be achieved as for ordered adsorbate layers, provided the data set is large enough.

The impact of variable sea ice roughness on changes in Arctic Ocean surface stress: a model study

The Arctic sea ice cover is thinning and retreating, causing changes in surface roughness that in turn modify the momentum flux from the atmosphere through the ice into the ocean. New model simulations comprising variable sea ice drag coefficients for both the air and water interface demonstrate that the heterogeneity in sea ice surface roughness significantly impacts the spatial distribution and trends of ocean surface stress during the last decades. Simulations with constant sea ice drag coefficients as used in most climate models show an increase in annual mean ocean surface stress (0.003 N/m2 per decade, 4.6%) due to the reduction of ice thickness leading to a weakening of the ice and accelerated ice drift. In contrast, with variable drag coefficients our simulations show annual mean ocean surface stress is declining at a rate of -0.002 N/m2 per decade (3.1%) over the period 1980-2013 because of a significant reduction in surface roughness associated with an increasingly thinner and younger sea ice cover. The effectiveness of sea ice in transferring momentum does not only depend on its resistive strength against the wind forcing but is also set by its top and bottom surface roughness varying with ice types and ice conditions. This reveals the need to account for sea ice surface roughness variations in climate simulations in order to correctly represent the implications of sea ice loss under global warming.

The relationship between absolute and proportion scores of serial order memory: simulation predictions and empirical data

The capability of a feature model of immediate memory (Nairne, 1990; Neath, 2000) to predict and account for a relationship between absolute and proportion scoring of immediate serial recall when memory load is varied (the list-length effect, LLE) is examined. The model correctly predicts the novel finding of an LLE in immediate serial order memory similar to that observed with free recall and previously assumed to be attributable to the long-term memory component of that procedure (Glanzer, 1972). The usefulness of formal models as predictive tools and the continuity between short-term serial order and longer term item memory are considered.

An efficient shock capturing algorithm for compressible flows in a duct of variable cross-section

A numerical scheme is presented for the solution of the Euler equations of compressible flow of a gas in a single spatial co-ordinate. This includes flow in a duct of variable cross-section as well as flow with slab, cylindrical or spherical symmetry and can prove useful when testing codes for the two-dimensional equations governing compressible flow of a gas. The resulting scheme requires an average of the flow variables across the interface between cells and for computational efficiency this average is chosen to be the arithmetic mean, which is in contrast to the usual ‘square root’ averages found in this type of scheme. The scheme is applied with success to five problems with either slab or cylindrical symmetry and a comparison is made in the cylindrical case with results from a two-dimensional problem with no sources.

Impact of variable atmospheric and oceanic form drag on simulations of Arctic sea ice

Over Arctic sea ice, pressure ridges and floe andmelt pond edges all introduce discrete obstructions to the flow of air or water past the ice and are a source of form drag. In current climate models form drag is only accounted for by tuning the air–ice and ice–ocean drag coefficients, that is, by effectively altering the roughness length in a surface drag parameterization. The existing approach of the skin drag parameter tuning is poorly constrained by observations and fails to describe correctly the physics associated with the air–ice and ocean–ice drag. Here, the authors combine recent theoretical developments to deduce the total neutral form drag coefficients from properties of the ice cover such as ice concentration, vertical extent and area of the ridges, freeboard and floe draft, and the size of floes and melt ponds. The drag coefficients are incorporated into the Los Alamos Sea Ice Model (CICE) and show the influence of the new drag parameterization on the motion and state of the ice cover, with the most noticeable being a depletion of sea ice over the west boundary of the Arctic Ocean and over the Beaufort Sea. The new parameterization allows the drag coefficients to be coupled to the sea ice state and therefore to evolve spatially and temporally. It is found that the range of values predicted for the drag coefficients agree with the range of values measured in several regions of the Arctic. Finally, the implications of the new form drag formulation for the spinup or spindown of the Arctic Ocean are discussed.

Detection of nitroaromatic vapours with diketopyrrolopyrrole thin films: exploring the role of structural order and morphology on thin film properties and fluorescence quenching efficiency

Sensitive optical detection of nitroaromatic vapours with diketo-pyrrolopyrrole thin films is reported for the first time and the impact of thin film crystal structure and morphology on fluorescence quenching behaviour demonstrated.

Synthesis and characterization of thermally stable second-order nonlinear optical side-chain polyimides containing thiazole and benzothiazole push-pull chromophores

Push-pull nonlinear optical (NLO) chromophores containing thiazole and benzothiazole acceptors were synthesized and characterized. Using these chromophores a series of second-order NLO polyimides were Successfully prepared from 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), pyromellitic dianhydride (PMDA) and 3,3'4,4'-benzophenone tetracarboxylic dianhydride (BTDA) by a standard condensation polymerization technique. These polyimides exhibit high glass transition temperatures ranging from 160 to 188 degrees C. UV-vis spectrum of polyimide exhibited a slight blue shift and decreases in absorption due to birefringence. From the order parameters, it was found that chromophores were aligned effectively. Using in situ poling and temperature ramping technique, the optical temperatures for corona poling were obtained. It was found that the optimal temperatures of polyimides approach their glass transition temperatures. These polyimides demonstrate relatively large d(33) values range between 35.15 and 45.20 pm/V at 532 nm. (C) 2008 Elsevier B.V. All rights reserved.

Interpreting the response of a dryland river system to Late Quaternary climate change

A U-series calcrete chronology has been constructed for three Late Quaternary terrace units, termed the D1, D2 and D3 terraces in age descending order, from the Rio Aguas river system of the Sorbas basin, southeast Spain. The D1 terrace formed between 30,300 +/- 4400 year BP and 12,140 +/- 360 year BP, correlating well with the Last Glacial Maximum when rates of sediment supply would have increased greatly, because of higher rates of weathering, reduced vegetation cover and weak soil development. The D2 terrace formed between 12,800 +/- 1100 year BP and 9,600 +/- 530 year BP, correlating well with the Younger Dryas event. The D3 terrace could only be poorly constrained to the early Holocene and no unequivocal cause could be assigned to this period of aggradation. The sedimentology and geomorphology of the D2 terrace suggests, however, that the aggradation of this unit was a response to diapirism/karstic processes occurring within the underlying Messinian gypsum strata and the subsequent damming of the Aguas system. Therefore, despite its coincident occurrence with the Younger Dryas, aggradation of the D2 terrace is unrelated to climate change. The style of this response, controlled predominantly by the characteristics of the underlying bedrock, makes correlating the terrace record of the Aguas with other systems in the Mediterranean unreliable. This study, therefore, highlights the problems of correlating fluvial sequences in regions of variable tectonics, climatic history and bedrock geology and emphasises the need to properly understand the main controls on individual fluvial systems before any attempt is made to correlate their depositional histories. (C) 2004 Elsevier Ltd. All rights reserved.

Redox-active polymers based on nonbridged metal−metal bonds. Electrochemical formation of [Os(bpy)(CO)(L)]n(bpy = 2,2‘-bipyridine; L = CO, MeCN) and of their reduced forms: a spectroelectrochemical study

IR, UV-vis, and EPR spectroelectrochemistry at variable temperatures and in different solvents were applied to investigate in situ the formation of electroactive molecular chains with a nonbridged Os-Os backbone, in particular, the polymer [Os-0(bpy)(CO)(2)](n), (bpy = 2,2'-bipyridine), from a mononuclear Os(II) carbonyl precursor, [Os-II(bpy)(CO)(2)Cl-2]. The one-electron-reduced form, [Os-II(bpy(.-))(CO)(2)Cl-2](-), has been characterized spectroscopically at low temperatures. This radical anion is the key intermediate in the electrochemical propagation process responsible for the metal-metal bond formation. Unambiguous spectroscopic evidence has been gained also for the formation of [{Os-0(bpy(.-))(CO)(2)}(-)](n), the electron-rich electrocatalyst of CO2 reduction. The polymer species are fairly well soluble in butyronitrile, which is important for their potential utilization in nanoscience, for example, as conducting molecular wires. We have also shown that complete solubility is accomplished for the monocarbonyl-acetonitrile derivative of the polymer, [Os-0(bpy)(CO)(MeCN)(2)Cl](n).

The synthesis of dicobalt and dinickel complexes of trimethylsilylethynyl-1, 2-dihydrofullerene; characterisation by n.m.r. and structure of the first acyclic metal fullerene derivative: molecular structure of [η2-{2-H-1-(Me3SiC ≡ C)-C60}Ni2(η-C5H5)2]

The synthesis and characterisation of the complexes [η2-{2-H-1-(Me3SiC ≡ C)-C60}Co2(CO)6] (2)} and [η-2-{2-H-1-(Me3SiC ≡ C)-C60}Ni2η-C5H5)2] (3)} is reported, together with a single-crystal molecular structure for (3). This provides the first structural data for an acyclic metal derivative of [60]-fullerene.