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.

Synthesis, structural characterization and electrochemical activity of oxidovanadium(IV/V) complexes of a diprotic ONS chelating ligand

The present work reports the chemistry of a few oxidovanadium(IV) and (V) complexes of the ONS chelating ligand S-benzyl-beta-N-(2-hydroxyphenylethylidine) dithiocarbazate (H2L). Major objective of this work is to arrive at some general conclusions about the influence of binding environment generated by the replacement of an O-donor center by a S-donor point in a ligand (of a similar arrangement of the other O- and N-donor points) on the redox behavior and on the structural features of comparable [VO(OEt)(ONS)] and [VO(OEt)(ONO)] complexes. Synthesis, characterization by various physicochemical techniques (UV-Vis, IR, EPR and elemental analysis), exploration of electrochemical activity of the oxidovanadium(V) complex [(VO)-O-V(OEt) L] (1), the mixed ligand complex [(VO)-O-V(N-O)L] (3) (where N-O is the mono anion of 8-hydroxyquinoline) and a binuclear complex [(VO)-O-V(OEt)L](2)(mu-4,4'-bipy) (2) are reported. Similar studies on of mixed ligand oxidovanadium(IV) complexes of the formula [(VO)-O-V(N-N)L] (4,5) (where N-N = 2,2'-bipy and o-phen) are also presented here. The [(VO)-O-V(OEt)L] complex is pentacoordinated and distorted square pyramidal, while the [V-IV(N-N)L] complexes are hexacoordinated and octahedral. Structural features of the complex 1 were compared with the corresponding aspects of the previously reported analogous complex [(VO)-O-V(OEt)(ONO)] (1').

The rise and fall of open solar flux during the current grand solar maximum

We use geomagnetic activity data to study the rise and fall over the past century of the solar wind flow speed VSW, the interplanetary magnetic field strength B, and the open solar flux FS. Our estimates include allowance for the kinematic effect of longitudinal structure in the solar wind flow speed. As well as solar cycle variations, all three parameters show a long-term rise during the first half of the 20th century followed by peaks around 1955 and 1986 and then a recent decline. Cosmogenic isotope data reveal that this constitutes a grand maximum of solar activity which began in 1920, using the definition that such grand maxima are when 25-year averages of the heliospheric modulation potential exceeds 600 MV. Extrapolating the linear declines seen in all three parameters since 1985, yields predictions that the grand maximum will end in the years 2013, 2014, or 2027 using VSW, FS, or B, respectively. These estimates are consistent with predictions based on the probability distribution of the durations of past grand solar maxima seen in cosmogenic isotope data. The data contradict any suggestions of a floor to the open solar flux: we show that the solar minimum open solar flux, kinematically corrected to allow for the excess flux effect, has halved over the past two solar cycles.

Phase mixing and phase separation accompanying the catalytic oxidation of CO on Ir{100}

The co-adsorption of CO and O on the unreconstructed (1 x 1) phase of Ir {100} was examined by low energy electron diffraction (LEED) and temperature programmed desorption (TPD). When CO is adsorbed at 188 K onto the Ir{100} surface precovered with 0.5 ML O, a mixed c(4 x 2)-(2O + CO) overlayer is formed. All CO is oxidised upon heating and desorbs as CO2 in three distinct stages at 230 K, 330 K and 430 K in a 2:1:2 ratio. The excess oxygen left on the surface after all CO has reacted forms an overlayer with a LEED pattern with p(2 x 10) periodicity. This overlayer consists of stripes with a local p(2 x 1)-O arrangement of oxygen atoms separated by stripes of uncovered It. When CO is adsorbed at 300 K onto the surface precovered with 0.5 ML O an apparent (2 x 2) LEED pattern is observed. LEED IV analysis reveals that this pattern is a superposition of diffraction patterns from islands of c(2 x 2)-CO and p(2 x 1)-O structures on the surface. Heating this co-adsorbed overlayer leads to the desorption of CO, in two stages at 330 K and 430 K; the excess CO (0.1 ML) desorbs at 590 K. LEED IV structural analysis of the mixed c(4 x 2) O and CO overlayer shows that both the CO molecules and the O atoms occupy bridge sites. The O atoms show significant lateral displacements of 0.14 angstrom away from the CO molecules; the C-O bond is slightly expanded with respect to the gas phase (1.19 angstrom); the modifications of the Ir substrate with respect to the bulk-terminated surface are very small. (c) 2006 Elsevier B.V. All rights reserved.

The neural basis of maternal responsiveness to infants: an fMRI study

Using fMRI, we examined the neural correlates of maternal responsiveness. Ten healthy mothers viewed alternating blocks of video: (i) 40 s of their own infant; (ii) 20 s of a neutral video; (iii) 40 s of an unknown infant and (iv) 20 s of neutral video, repeated 4 times. Predominant BOLD signal change to the contrast of infants minus neutral stimulus occurred in bilateral visual processing regions BA minus neutral stimulus occurred in bilateral visual processing regions (BA 38), left amygdala and visual cortex (BA 19), and to the unknown infant minus own infant contrast in bilateral orbitofrontal cortex (BA 10,47) and medial prefrontal cortex (BA 8). These findings suggest that amygdala and temporal pole may be key sites in mediating a mother's response to her infant and reaffirms their importance in face emotion processing and social behaviour.

Abundance and diversity of wild bees along gradients of heavy metal pollution

1. Wild bees are one of the most important groups of pollinators in the temperate zone. Therefore, population declines have potentially negative impacts for both crop and wildflower pollination. Although heavy metal pollution is recognized to be a problem affecting large parts of the European Union, we currently lack insights into the effects of heavy metals on wild bees. 2. We investigated whether heavy metal pollution is a potential threat to wild bee communities by comparing (i) species number, (ii) diversity and (iii) abundance as well as (iv) natural mortality of emerging bees along two independent gradients of heavy metal pollution, one at Olkusz (OLK), Poland and the other at Avonmouth (AVO), UK. We used standardized nesting traps to measure species richness and abundance of wild bees, and we recorded the heavy metal concentration in pollen collected by the red mason bee Osmia rufa as a measure of pollution. 3. The concentration of cadmium, lead and zinc in pollen collected by bees ranged from a background level in unpolluted sites [OLK: 1·3, 43·4, 99·8 (mg kg−1); AVO: 0·8, 42·0, 56·0 (mg kg−1), respectively] to a high level on sites in the vicinity of the OLK and AVO smelters [OLK: 6·7, 277·0, 440·1 (mg kg−1); AVO: 9·3, 356·2, 592·4 (mg kg−1), respectively]. 4. We found that with increasing heavy metal concentration, there was a steady decrease in the number, diversity and abundance of solitary, wild bees. In the most polluted sites, traps were empty or contained single occupants, whereas in unpolluted sites, the nesting traps collected from 4 to 5 species represented by up to ten individuals. Moreover, the proportion of dead individuals of the solitary bee Megachile ligniseca increased along the heavy metal pollution gradient at OLK from 0·2 in uncontaminated sites to 0·5 in sites with a high concentration of pollution. 5. Synthesis and applications. Our findings highlight the negative relationship between heavy metal pollution and populations of wild bees and suggest that increasing wild bee richness in highly contaminated areas will require special conservation strategies. These may include creating suitable nesting sites and sowing a mixture of flowering plants as well as installing artificial nests with wild bee cocoons in polluted areas. Applying protection plans to wild pollinating bee communities in heavy metal-contaminated areas will contribute to integrated land rehabilitation to minimize the impact of pollution on the environment.

Complete Experimental Structure Determination of the p(3x2)pg Phase of Glycine on Cu{110}

We present a quantitative low energy electron diffraction (LEED) surface-crystallograpic study of the complete adsorption geometry of glycine adsorbed on Cu{110} in the ordered p(3×2) phase. The glycine molecules form bonds to the surface through the N atoms of the amino group and the two O atoms of the de-protonated carboxylate group, each with separate Cu atoms such that every Cu atom in the first layer is involved in a bond. Laterally, N atoms are nearest to the atop site (displacement 0.41 Å). The O atoms are asymmetrically displaced from the atop site by 0.54 Å and 1.18 Å with two very different O-Cu bond lengths of 1.93 Å and 2.18 Å. The atom positions of the upper-most Cu layers show small relaxations within 0.07 Å of the bulk-truncated surface geometry. The unit cell of the adsorbate layer consists of two glycine molecules, which are related by a glide-line symmetry operation. This study clearly shows that a significant coverage of adsorbate structures without this glide-line symmetry must be rejected, both on the grounds of the energy dependence of the spot intensities (LEED-IV curves) and of systematic absences in the LEED pattern.

The impact of North Atlantic sea surface temperature errors on the simulation of North Atlantic European region climate

Current state-of-the-art climate models fail to capture accurately the path of the Gulf Stream and North Atlantic Current. This leads to a warm bias near the North American coast, where the modelled Gulf Stream separates from the coast further north, and a cold anomaly to the east of the Grand Banks of Newfoundland, where the North Atlantic Current remains too zonal in this region. Using an atmosphere-only model forced with the sea surface temperature (SST) biases in the North Atlantic, we consider the impact they have on the mean state and the variability in the North Atlantic European region in winter. Our results show that the SST errors produce a mean sea-level pressure response that is similar in magnitude and pattern to the atmospheric circulation errors in the coupled climate model. The work also suggests that errors in the coupled model storm tracks and North Atlantic Oscillation, compared to reanalysis data, can also be explained partly by these SST errors. Our results suggest that both the error in the Gulf Stream separation location and the path of the North Atlantic Current around the Grand Banks play important roles in affecting the atmospheric circulation. Reducing these coupled model errors could improve significantly the representation of the large-scale atmospheric circulation of the North Atlantic and European region.

Toward a new generation of world climate research and computing facilities

The impending threat of global climate change and its regional manifestations is among the most important and urgent problems facing humanity. Society needs accurate and reliable estimates of changes in the probability of regional weather variations to develop science-based adaptation and mitigation strategies. Recent advances in weather prediction and in our understanding and ability to model the climate system suggest that it is both necessary and possible to revolutionize climate prediction to meet these societal needs. However, the scientific workforce and the computational capability required to bring about such a revolution is not available in any single nation. Motivated by the success of internationally funded infrastructure in other areas of science, this paper argues that, because of the complexity of the climate system, and because the regional manifestations of climate change are mainly through changes in the statistics of regional weather variations, the scientific and computational requirements to predict its behavior reliably are so enormous that the nations of the world should create a small number of multinational high-performance computing facilities dedicated to the grand challenges of developing the capabilities to predict climate variability and change on both global and regional scales over the coming decades. Such facilities will play a key role in the development of next-generation climate models, build global capacity in climate research, nurture a highly trained workforce, and engage the global user community, policy-makers, and stakeholders. We recommend the creation of a small number of multinational facilities with computer capability at each facility of about 20 peta-flops in the near term, about 200 petaflops within five years, and 1 exaflop by the end of the next decade. Each facility should have sufficient scientific workforce to develop and maintain the software and data analysis infrastructure. Such facilities will enable questions of what resolution, both horizontal and vertical, in atmospheric and ocean models, is necessary for more confident predictions at the regional and local level. Current limitations in computing power have placed severe limitations on such an investigation, which is now badly needed. These facilities will also provide the world's scientists with the computational laboratories for fundamental research on weather–climate interactions using 1-km resolution models and on atmospheric, terrestrial, cryospheric, and oceanic processes at even finer scales. Each facility should have enabling infrastructure including hardware, software, and data analysis support, and scientific capacity to interact with the national centers and other visitors. This will accelerate our understanding of how the climate system works and how to model it. It will ultimately enable the climate community to provide society with climate predictions, which are based on our best knowledge of science and the most advanced technology.

Glacial-interglacial temperature change in the tropical West Pacific: a comparison of stalagmite-based paleo-thermometers

In the tropics, geochemical records from stalagmites have so far mainly been used to qualitatively reconstruct changes in precipitation, but several new methods to reconstruct past temperatures from stalagmite material have emerged recently: i) liquid–vapor homogenization of fluid inclusion water ii) noble gas concentrations in fluid inclusion water, iii) the partitioning of oxygen isotopes between fluid inclusion water and calcite, and iv) the abundance of the 13C18O16O (‘clumped’) isotopologue in calcite. We present, for the first time, a direct comparison of these four paleo-thermometers by applying them to a fossil stalagmite covering nearly two glacial–interglacial cycles (Marine Isotope Stages (MIS) 12–9) and to two modern stalagmites, all from northern Borneo. The temperature estimates from the different methods agree in most cases within errors for both the old and recent samples; reconstructed formation temperatures of the recent samples match within 2-sigma errors with measured cave temperatures. However, slight but systematic deviations are observed between noble gas and liquid–vapor homogenization temperatures. Whereas the temperature sensitivity of fluid inclusion δ18O and clumped isotopes is currently debated, we find that the calibration of Tremaine et al. (2011) for fluid inclusion δ18O and a synthetic calcite-based clumped isotope calibration (Ziegler et al., in prep.) yield temperature estimates consistent with the other methods. All methods (with the potential exception of clumped isotopes) show excellent agreement on the amplitude of glacial–interglacial temperature change, indicating temperature shifts of 4–5 °C. This amplitude is similar to the amplitude of Mg/Ca-based regional sea surface temperature records, when correcting for sea level driven changes in cave elevation. Our reconstruction of tropical temperature evolution over the time period from 440 to 320 thousand years ago (ka) adds support to the view that climate sensitivity to varying greenhouse forcing is substantial also in the deep tropics.

Chinese overseas doctoral student narratives of intercultural adaptation

This study aims to explore how Chinese overseas doctoral students adjust to a different academic, social and cultural environment, using Giddens’ theoretical framework of self-identity (1991). The findings indicate the participants proactively used various coping strategies in meeting challenges, and adapting to new social environments. Continuity and stability of self-identity were achieved either culturally or academically through self-reflexivity, autonomy, creativity, authenticity, and reliance on an ontological identity. The result is to challenge the grand narrative of essentialised “problematic Chinese learners”.

A new calibrated sunspot group series since 1749: statistics of active day fractions

Although the sunspot-number series have existed since the mid-19th century, they are still the subject of intense debate, with the largest uncertainty being related to the "calibration" of the visual acuity of individual observers in the past. Daisy-chain regression methods are applied to inter-calibrate the observers which may lead to significant bias and error accumulation. Here we present a novel method to calibrate the visual acuity of the key observers to the reference data set of Royal Greenwich Observatory sunspot groups for the period 1900-1976, using the statistics of the active-day fraction. For each observer we independently evaluate their observational thresholds [S_S] defined such that the observer is assumed to miss all of the groups with an area smaller than S_S and report all the groups larger than S_S. Next, using a Monte-Carlo method we construct, from the reference data set, a correction matrix for each observer. The correction matrices are significantly non-linear and cannot be approximated by a linear regression or proportionality. We emphasize that corrections based on a linear proportionality between annually averaged data lead to serious biases and distortions of the data. The correction matrices are applied to the original sunspot group records for each day, and finally the composite corrected series is produced for the period since 1748. The corrected series displays secular minima around 1800 (Dalton minimum) and 1900 (Gleissberg minimum), as well as the Modern grand maximum of activity in the second half of the 20th century. The uniqueness of the grand maximum is confirmed for the last 250 years. It is shown that the adoption of a linear relationship between the data of Wolf and Wolfer results in grossly inflated group numbers in the 18th and 19th centuries in some reconstructions.