Lithium and oxygen adsorption at the b-MnO2 (110) surface

The adsorption and co-adsorption of lithium and oxygen at the surface of rutile-like manganese dioxide(b-MnO2), which are important in the context of Li–air batteries, are investigated using density functional theory. In the absence of lithium, the most stable surface of b-MnO2, the (110), adsorbs oxygen in the form of peroxo groups bridging between two manganese cations. Conversely, in the absence of excess oxygen, lithium atoms adsorb on the (110) surface at two different sites, which are both tricoordinated to surface oxygen anions, and the adsorption always involves the transfer of one electron from the adatom to one of the five-coordinated manganese cations at the surface, creating (formally) Li+ and Mn3+ species. The co-adsorption of lithium and oxygen leads to the formation of a surface oxide, involving the dissociation of the O2 molecule, where the O adatoms saturate the coordination of surface Mn cations and also bind to the Li adatoms. This process is energetically more favourable than the formation of gas-phase lithium peroxide (Li2O2) monomers, but less favourable than the formation of Li2O2 bulk. These results suggest that the presence of b-MnO2 in the cathode of a nonaqueous Li–O2 battery lowers the energy for the initial reduction of oxygen during cell discharge.

On the radius of centrality in evolving communication networks

In this article, we investigate how the choice of the attenuation factor in an extended version of Katz centrality influences the centrality of the nodes in evolving communication networks. For given snapshots of a network, observed over a period of time, recently developed communicability indices aim to identify the best broadcasters and listeners (receivers) in the network. Here we explore the attenuation factor constraint, in relation to the spectral radius (the largest eigenvalue) of the network at any point in time and its computation in the case of large networks. We compare three different communicability measures: standard, exponential, and relaxed (where the spectral radius bound on the attenuation factor is relaxed and the adjacency matrix is normalised, in order to maintain the convergence of the measure). Furthermore, using a vitality-based measure of both standard and relaxed communicability indices, we look at the ways of establishing the most important individuals for broadcasting and receiving of messages related to community bridging roles. We compare those measures with the scores produced by an iterative version of the PageRank algorithm and illustrate our findings with two examples of real-life evolving networks: the MIT reality mining data set, consisting of daily communications between 106 individuals over the period of one year, a UK Twitter mentions network, constructed from the direct \emph{tweets} between 12.4k individuals during one week, and a subset the Enron email data set.

Bridge-localized HOMO-binding character of divinylanthracene-bridged dinuclear ruthenium carbonyl complexes: spectroscopic, spectroelectrochemical, and computational studies

The electronic properties of four divinylanthracene-bridged diruthenium carbonyl complexes [{RuCl(CO)(PMe3)3}2(μ[BOND]CH[DOUBLE BOND]CHArCH[DOUBLE BOND]CH)] (Ar=9,10-anthracene (1), 1,5-anthracene (2), 2,6-anthracene (3), 1,8-anthracene (4)) obtained by molecular spectroscopic methods (IR, UV/Vis/near-IR, and EPR spectroscopy) and DFT calculations are reported. IR spectroelectrochemical studies have revealed that these complexes are first oxidized at the noninnocent bridging ligand, which is in line with the very small ν(C[TRIPLE BOND]O) wavenumber shift that accompanies this process and also supported by DFT calculations. Because of poor conjugation in complex 1, except oxidized 1+, the electronic absorption spectra of complexes 2+, 3+, and 4+ all display the characteristic near-IR band envelopes that have been deconvoluted into three Gaussian sub-bands. Two of the sub-bands belong mainly to metal-to-ligand charge-transfer (MLCT) transitions according to results from time-dependent DFT calculations. EPR spectroscopy of chemically generated 1+–4+ proves largely ligand-centered spin density, again in accordance with IR spectra and DFT calculations results.

Categories, concepts and units: representing energy demand in and through time

Methods of data collection are unavoidably rooted in some sort of theoretical paradigm, and are inextricably tied to an implicit agenda or broad problem framing. These prior orientations are not always explicit, but they matter for what data is collected and how it is used. They also structure opportunities for asking new questions, for linking or bridging between existing data sets and they matter even more when data is re-purposed for uses not initially anticipated. In this paper we provide an historical and comparative review of the changing categories used in organising and collecting data on mobility/travel and time use as part of ongoing work to understand, conceptualise and describe the changing patterns of domestic and mobility related energy demand within UK society. This exercise reveals systematic differences of method and approach, for instance in units of measurement, in how issues of time/duration and periodicity are handled, and how these strategies relate to the questions such data is routinely used to address. It also points to more fundamental differences in how traditions of research into mobility, domestic energy and time use have developed. We end with a discussion of the practical implications of these diverse histories for understanding and analysing changing patterns of energy/mobility demand at different scales.

An assessment of the impact of local processes on dust lifting in martian climate models

Simulation of the lifting of dust from the planetary surface is of substantially greater importance on Mars than on Earth, due to the fundamental role that atmospheric dust plays in the former’s climate, yet the dust emission parameterisations used to date in martian global climate models (MGCMs) lag, understandably, behind their terrestrial counterparts in terms of sophistication. Recent developments in estimating surface roughness length over all martian terrains and in modelling atmospheric circulations at regional to local scales (less than O(100 km)) presents an opportunity to formulate an improved wind stress lifting parameterisation. We have upgraded the conventional scheme by including the spatially varying roughness length in the lifting parameterisation in a fully consistent manner (thereby correcting a possible underestimation of the true threshold level for wind stress lifting), and used a modification to account for deviations from neutral stability in the surface layer. Following these improvements, it is found that wind speeds at typical MGCM resolution never reach the lifting threshold at most gridpoints: winds fall particularly short in the southern midlatitudes, where mean roughness is large. Sub-grid scale variability, manifested in both the near-surface wind field and the surface roughness, is then considered, and is found to be a crucial means of bridging the gap between model winds and thresholds. Both forms of small-scale variability contribute to the formation of dust emission ‘hotspots’: areas within the model gridbox with particularly favourable conditions for lifting, namely a smooth surface combined with strong near-surface gusts. Such small-scale emission could in fact be particularly influential on Mars, due both to the intense positive radiative feedbacks that can drive storm growth and a strong hysteresis effect on saltation. By modelling this variability, dust lifting is predicted at the locations at which dust storms are frequently observed, including the flushing storm sources of Chryse and Utopia, and southern midlatitude areas from which larger storms tend to initiate, such as Hellas and Solis Planum. The seasonal cycle of emission, which includes a double-peaked structure in northern autumn and winter, also appears realistic. Significant increases to lifting rates are produced for any sensible choices of parameters controlling the sub-grid distributions used, but results are sensitive to the smallest scale of variability considered, which high-resolution modelling suggests should be O(1 km) or less. Use of such models in future will permit the use of a diagnosed (rather than prescribed) variable gustiness intensity, which should further enhance dust lifting in the southern hemisphere in particular.

Hybrid materials through linkage of chalcogenide tetrahedral clusters

Tetrahedral chalcogenide clusters, with their well-defined molecular structures and interesting properties, are attractive building blocks for hybrid materials, in which porosity may be integrated with electronic or optical properties. Linkage of tetrahedral clusters often occurs through bridging chalcogenolate ligands, and results in extended structures of inorganic connectivity. However, linkage of tetrahedral clusters via organic ligands is also possible and a number of coordination polymers have already been reported. Recent advances on the synthesis and crystal structures of extended hybrid structures based on tetrahedral clusters are described here.

Modelling the rheology of anisotropic particles adsorbed on a two-dimensional fluid interface

We present a general approach based on nonequilibrium thermodynamics for bridging the gap between a well-defined microscopic model and the macroscopic rheology of particle-stabilised interfaces. Our approach is illustrated by starting with a microscopic model of hard ellipsoids confined to a planar surface, which is intended to simply represent a particle-stabilised fluid–fluid interface. More complex microscopic models can be readily handled using the methods outlined in this paper. From the aforementioned microscopic starting point, we obtain the macroscopic, constitutive equations using a combination of systematic coarse-graining, computer experiments and Hamiltonian dynamics. Exemplary numerical solutions of the constitutive equations are given for a variety of experimentally relevant flow situations to explore the rheological behaviour of our model. In particular, we calculate the shear and dilatational moduli of the interface over a wide range of surface coverages, ranging from the dilute isotropic regime, to the concentrated nematic regime.

Processing of zero-derived words in English: an fMRI investigation

Derivational morphological processes allow us to create new words (e.g. punish (V) to noun (N) punishment) from base forms. The number of steps from the basic units to derived words often varies (e.g., nationalitybridge-V) i.e., zero-derivation ( Aronoff, 1980). We compared the processing of one-step (soakingbridgingbridging) in a lexical decision task. Although the surface derived -ing forms can be contextually participles, gerunds, or even nouns, they are all derived from verbs since the suffix -ing can only be attached to verb roots. Crucially, the verb root is the basic form for the one-step words, whereas for the two-step words the verb root is zero derived from a basic noun. Significantly increased brain activity was observed for complex (one-step and two-step) versus simple (zero-step) forms in regions involved in morphological processing, such as the left inferior frontal gyrus (LIFG). Critically, activation was also more pronounced for two-step compared to one-step forms. Since both types of derived words have the same surface structure, our findings suggest that morphological processing is based on underlying morphological complexity, independent of overt affixation. This study is the first to provide evidence for the processing of zero derivation, and demonstrates that morphological processing cannot be reduced to surface form-based segmentation.

Adaptive governance: livelihood innovation for climate resilience in Uganda

Adaptive governance is the use of novel approaches within policy to support experimentation and learning. Social learning reflects the engagement of interdependent stakeholders within this learning. Much attention has focused on these concepts as a solution for resilience in governing institutions in an uncertain climate; resilience representing the ability of a system to absorb shock and to retain its function and form through reorganisation. However, there are still many questions to how these concepts enable resilience, particularly in vulnerable, developing contexts. A case study from Uganda presents how these concepts promote resilient livelihood outcomes among rural subsistence farmers within a decentralised governing framework. This approach has the potential to highlight the dynamics and characteristics of a governance system which may manage change. The paper draws from the enabling characteristics of adaptive governance, including lower scale dynamics of bonding and bridging ties and strong leadership. Central to these processes were learning platforms promoting knowledge transfer leading to improved self-efficacy, innovation and livelihood skills. However even though aspects of adaptive governance were identified as contributing to resilience in livelihoods, some barriers were identified. Reflexivity and multi-stakeholder collaboration were evident in governing institutions; however, limited self-organisation and vertical communication demonstrated few opportunities for shifts in governance, which was severely challenged by inequity, politicisation and elite capture. The paper concludes by outlining implications for climate adaptation policy through promoting the importance of mainstreaming adaptation alongside existing policy trajectories; highlighting the significance of collaborative spaces for stakeholders and the tackling of inequality and corruption.

Production of definite and indefinite articles in typically developing English-speaking children and children with SLI

The present paper examines the production of definite and indefinite articles in English-speaking typically developing (TD) children and children with Specific Language Impairment (SLI). Twenty four English-speaking children with SLI (mean age: 7;5), twenty nine TD age-matched (TD-AM) children (mean age: 7;5) and eleven younger (mean age: 5;5) TD vocabulary-matched (TD-VM) children participated in a production task involving short stories without picture props based on Schafer and de Villiers (2000). Article production was examined in two different semantic contexts for the definite article, namely in the anaphoric and the bridging context. In the anaphoric condition, definiteness is established via linguistic means, whereas in the bridging condition via shared world knowledge. Indefinite article production was examined in the referential specific, non-referential predicational, and non-referential instrumental contexts. The referential specific context involves [+speaker, −hearer] knowledge and the non-referential predicational and instrumental [−speaker, −hearer] knowledge. Results showed that in the definite article contexts, all three groups performed better on the bridging compared with the anaphoric condition; in the indefinite article contexts, they had better performance on the non-referential predicational vs. the referential specific and the non-referential instrumental conditions. In terms of errors, the TD-VM children and the children with SLI produced significantly more substitutions than the TD-AM children in the definite article contexts. In the indefinite article contexts, the three groups did not differ in terms of accuracy or error patterns. The present results point towards problems in the discourse integration of entities that are part of the speaker's and hearer's knowledge in children with SLI and TD-VM controls, especially in definite articles. These problems are accentuated in the children with SLI due to their grammatical impairment and suggest that children with SLI exhibit a delayed acquisition profile.

Production and on-line comprehension of definiteness in English and Dutch by monolingual and sequential bilingual children

The present article examines production and on-line processing of definite articles in Turkish-speaking sequential bilingual children acquiring English and Dutch as second languages (L2) in the UK and in the Netherlands, respectively. Thirty-nine 6–8-year-old L2 children and 48 monolingual (L1) age-matched children participated in two separate studies examining the production of definite articles in English and Dutch in conditions manipulating semantic context, that is, the anaphoric and the bridging contexts. Sensitivity to article omission was examined in the same groups of children using an on-line processing task involving article use in the same semantic contexts as in the production task. The results indicate that both L2 children and L1 controls are less accurate when definiteness is established by keeping track of the discourse referents (anaphoric) than when it is established via world knowledge (bridging). Moreover, despite variable production, all groups of children were sensitive to the omission of definite articles in the on-line comprehension task. This suggests that the errors of omission are not due to the lack of abstract syntactic representations, but could result from processes implicated in the spell-out of definite articles. The findings are in line with the idea that variable production in child L2 learners does not necessarily indicate lack of abstract representations (Haznedar and Schwartz, 1997).

From warfare to welfare: veterans, military charities and the blurred spatiality of post-service welfare in the United Kingdom

The military offers a form of welfare-for-work but when personnel leave they lose this safety net, a loss exacerbated by the rollback neoliberalism of the contemporary welfare state. Increasingly the third sector has stepped in to address veterans’ welfare needs through operating within and across military/civilian and state/market/community spaces and cultures. In this paper we use both veterans’ and military charities’ experiences to analyse the complex politics that govern the liminal boundary zone of post-military welfare. Through exploring ‘crossing’ and ‘bridging’ we conceptualise military charities as ‘boundary subjects’, active yet dependent on the continuation of the civilian-military binary, and argue that the latter is better understood as a multidirectional, multiscalar and contextual continuum. Post-military welfare emerges as a competitive, confused and confusing assemblage that needs to be made more navigable in order to better support the ‘heroic poor’.

Advancements in decadal climate predictability: the role of nonoceanic drivers

We review recent progress in understanding the role of sea ice, land surface, stratosphere, and aerosols in decadal-scale predictability and discuss the perspectives for improving the predictive capabilities of current Earth system models (ESMs). These constituents have received relatively little attention because their contribution to the slow climatic manifold is controversial in comparison to that of the large heat capacity of the oceans. Furthermore, their initialization as well as their representation in state-of-the-art climate models remains a challenge. Numerous extraoceanic processes that could be active over the decadal range are proposed. Potential predictability associated with the aforementioned, poorly represented, and scarcely observed constituents of the climate system has been primarily inspected through numerical simulations performed under idealized experimental settings. The impact, however, on practical decadal predictions, conducted with realistically initialized full-fledged climate models, is still largely unexploited. Enhancing initial-value predictability through an improved model initialization appears to be a viable option for land surface, sea ice, and, marginally, the stratosphere. Similarly, capturing future aerosol emission storylines might lead to an improved representation of both global and regional short-term climatic changes. In addition to these factors, a key role on the overall predictive ability of ESMs is expected to be played by an accurate representation of processes associated with specific components of the climate system. These act as “signal carriers,” transferring across the climatic phase space the information associated with the initial state and boundary forcings, and dynamically bridging different (otherwise unconnected) subsystems. Through this mechanism, Earth system components trigger low-frequency variability modes, thus extending the predictability beyond the seasonal scale.

Notable differences between oxidized diruthenium complexes bridged by four isomeric diethynyl benzodithiophene ligands

Four new diruthenium complexes [{(η5-C5Me5)Ru(dppe)}2(μ-CuC–L–CuC)] featuring different bridging isomeric diethynyl benzodithiophenes viz. L = benzo[1,2-b;4,5-b’]dithiophene (complex 1), benzo[2,1-b;4,5b’]dithiophene (complex 2), benzo[1,2-b;3,4-b’]dithiophene (complex 3) and benzo[1,2-b;4,3-b’]-dithiophene (complex 4), were synthesized and characterized by molecular spectroscopic and crystallographicmethods. The subtle changes in the molecular structure introduced by the diethynyl benzodithiophene isomers have a notable impact on the stability of the oxidized complexes and their absorption characteristics in the visible-NIR and IR spectral domains. Electronic properties of stable oxidized complexes[1]n+ and [4]n+ (n = 1, 2) were investigated by cyclic voltammetry, UV-vis-NIR and IR spectroelectrochemistry as well as DFT and TDDFT calculations. The results document the largely bridgelocalized character of the oxidation of parents 1 and 4. Cations [2]+ and [3]+ are too unstable at ambient temperature to afford their unambiguous characterization. UV-vis-NIR absorption spectral data combined with TDDFT calculations (BLYP35) reveal that the broad electronic absorption of [1]+ and [4]+ in the NIR region has a mixed intraligand π–π* and MLCT character, with similar contribution from their spin-delocalized trans and cis conformers. A spin-localized (mixed-valence) rotamer was only observed for [1]+ at ambient temperature as a minor component on the time scale of IR spectroscopy.

Equilibrium behavior of symmetric ABA triblock copolymer melts

Melts of ABA triblock copolymer molecules with identical end blocks are examined using self-consistent field theory (SCFT). Phase diagrams are calculated and compared with those of homologous AB diblock copolymers formed by snipping the triblocks in half. This creates additional end segments which decreases the degree of segregation. Consequently, triblock melts remain ordered to higher temperatures than their diblock counterparts. We also find that middle-block domains are easier to stretch than end-block domains. As a result, domain spacings are slightly larger, the complex phase regions are shifted towards smaller A-segment compositions, and the perforated-lamellar phase becomes more metastable in triblock melts as compared to diblock melts. Although triblock and diblock melts exhibit very similar phase behavior, their mechanical properties can differ substantially due to triblock copolymers that bridge between otherwise disconnected A domains. We evaluate the bridging fraction for lamellar, cylindrical, and spherical morphologies to be about 40%–45%, 60%–65%, and 75%–80%, respectively. These fractions only depend weakly on the degree of segregation and the copolymer composition.