A rare case of solution and solid state inter-conversion of two copper(II) dimers and a copper(II) chain

Three Cu(II)-azido complexes of formula [Cu2L2(N-3)(2)] (1), [Cu2L2(N-3)(2)]center dot H2O (2) and [CuL(N-3)](n) (3) have been synthesized using the same tridentate Schiff base ligand HL (2-[(3-methylaminopropylimino)-methyl]-phenol), the condensation product of N-methyl-1,3-propanediamine and salicyldehyde). Compounds 1 and 2 are basal-apical mu-1,1 double azido bridged dimers. The dimeric structure of 1 is centro-symmetric but that of 2 is non-centrommetric. Compound 3 is a mu-1,1 single azido bridged 1D chain. The three complexes interconvert in solution and can be obtained in pure form by carefully controlling the synthetic conditions. Compound 2 undergoes an irreversible transformation to 1 upon dehydration in the solid state. The magnetic properties of compounds 1 and 2 show the presence of weak antiferromagnetic exchange interactions mediated by the double 1,1-N-3 azido bridges (J = -2.59(4) and -0.10(1) cm-(1), respectively). The single 1,1-N-3 bridge in compound 3 mediates a negligible exchange interaction.

Recent Glacier Retreat Exceeds Internal Variability

Glacier fluctuations exclusively due to internal variations in the climate system are simulated using downscaled integrations of the ECHAM4/OPYC coupled general circulation model (GCM). A process-based modeling approach using a mass balance model of intermediate complexity and a dynamic ice flow model considering simple shearing flow and sliding are applied. Multimillennia records of glacier length fluctuations for Nigardsbreen (Norway) and Rhonegletscher (Switzerland) are simulated using autoregressive processes determined by statistically downscaled GCM experiments. Return periods and probabilities of specific glacier length changes using GCM integrations excluding external forcings such as solar irradiation changes, volcanic, or anthropogenic effects are analyzed and compared to historical glacier length records. Preindustrial fluctuations of the glaciers as far as observed or reconstructed, including their advance during the “Little Ice Age,” can be explained by internal variability in the climate system as represented by a GCM. However, fluctuations comparable to the present-day glacier retreat exceed any variation simulated by the GCM control experiments and must be caused by external forcing, with anthropogenic forcing being a likely candidate.

Irreversible compressible work and APE dissipation in turbulent stratified fluid

Although it plays a key role in the theory of stratified turbulence, the concept of available potential energy (APE) dissipation has remained until now a rather mysterious quantity, owing to the lack of rigorous result about its irreversible character or energy conversion type. Here, we show by using rigorous energetics considerations rooted in the analysis of the Navier-Stokes for a fully compressible fluid with a nonlinear equation of state that the APE dissipation is an irreversible energy conversion that dissipates kinetic energy into internal energy, exactly as viscous dissipation. These results are established by showing that APE dissipation contributes to the irreversible production of entropy, and by showing that it is a part of the work of expansion/contraction. Our results provide a new interpretation of the entropy budget, that leads to a new exact definition of turbulent effective diffusivity, which generalizes the Osborn-Cox model, as well as a rigorous decomposition of the work of expansion/contraction into reversible and irreversible components. In the context of turbulent mixing associated with parallel shear flow instability, our results suggests that there is no irreversible transfer of horizontal momentum into vertical momentum, as seems to be required when compressible effects are neglected, with potential consequences for the parameterisations of momentum dissipation in the coarse-grained Navier-Stokes equations.

Available potential energy density for a multicomponent Boussinesq fluid with arbitrary nonlinear equation of state

In this paper, the concept of available potential energy (APE) density is extended to a multicomponent Boussinesq fluid with a nonlinear equation of state. As shown by previous studies, the APE density is naturally interpreted as the work against buoyancy forces that a parcel needs to perform to move from a notional reference position at which its buoyancy vanishes to its actual position; because buoyancy can be defined relative to an arbitrary reference state, so can APE density. The concept of APE density is therefore best viewed as defining a class of locally defined energy quantities, each tied to a different reference state, rather than as a single energy variable. An important result, for which a new proof is given, is that the volume integrated APE density always exceeds Lorenz’s globally defined APE, except when the reference state coincides with Lorenz’s adiabatically re-arranged reference state of minimum potential energy. A parcel reference position is systematically defined as a level of neutral buoyancy (LNB): depending on the nature of the fluid and on how the reference state is defined, a parcel may have one, none, or multiple LNB within the fluid. Multiple LNB are only possible for a multicomponent fluid whose density depends on pressure. When no LNB exists within the fluid, a parcel reference position is assigned at the minimum or maximum geopotential height. The class of APE densities thus defined admits local and global balance equations, which all exhibit a conversion with kinetic energy, a production term by boundary buoyancy fluxes, and a dissipation term by internal diffusive effects. Different reference states alter the partition between APE production and dissipation, but neither affect the net conversion between kinetic energy and APE, nor the difference between APE production and dissipation. We argue that the possibility of constructing APE-like budgets based on reference states other than Lorenz’s reference state is more important than has been previously assumed, and we illustrate the feasibility of doing so in the context of an idealised and realistic oceanic example, using as reference states one with constant density and another one defined as the horizontal mean density field; in the latter case, the resulting APE density is found to be a reasonable approximation of the APE density constructed from Lorenz’s reference state, while being computationally cheaper.

Ice internal friction: Standard theoretical perspectives on friction codified, adapted for the unusual rheology of ice, and unified

Sea ice contains flaws including frictional contacts. We aim to describe quantitatively the mechanics of those contacts, providing local physics for geophysical models. With a focus on the internal friction of ice, we review standard micro-mechanical models of friction. The solid's deformation under normal load may be ductile or elastic. The shear failure of the contact may be by ductile flow, brittle fracture, or melting and hydrodynamic lubrication. Combinations of these give a total of six rheological models. When the material under study is ice, several of the rheological parameters in the standard models are not constant, but depend on the temperature of the bulk, on the normal stress under which samples are pressed together, or on the sliding velocity and acceleration. This has the effect of making the shear stress required for sliding dependent on sliding velocity, acceleration, and temperature. In some cases, it also perturbs the exponent in the normal-stress dependence of that shear stress away from the value that applies to most materials. We unify the models by a principle of maximum displacement for normal deformation, and of minimum stress for shear failure, reducing the controversy over the mechanism of internal friction in ice to the choice of values of four parameters in a single model. The four parameters represent, for a typical asperity contact, the sliding distance required to expel melt-water, the sliding distance required to break contact, the normal strain in the asperity, and the thickness of any ductile shear zone.

Direct probing of photoinduced electron transfer in a self- assembled biomimetic [2Fe2S]-hydrogenase complex using ultrafast vibrational spectroscopy

A pyridyl-functionalized diiron dithiolate complex, [μ-(4-pyCH2−NMI-S2)Fe2(CO)6] (3, py = pyridine(ligand), NMI = naphthalene monoimide) was synthesized and fully characterized. In the presence of zinc tetraphenylporphyrin (ZnTPP), a self-assembled 3·ZnTPP complex was readily formed in CH2Cl2 by the coordination of the pyridyl nitrogen to the porphyrin zinc center. Ultrafast photoinduced electron transfer from excited ZnTPP to complex 3 in the supramolecular assembly was observed in real time by monitoring the ν(CO) and ν(CO)NMI spectral changes with femtosecond time-resolved infrared (TRIR) spectroscopy. We have confirmed that photoinduced charge separation produced the monoreduced species by comparing the time-resolved IR spectra with the conventional IR spectra of 3•− generated by reversible electrochemical reduction. The lifetimes for the charge separation and charge recombination processes were found to be τCS = 40 ± 3 ps and τCR = 205 ± 14 ps, respectively. The charge recombination is much slower than that in an analogous covalent complex, demonstrating the potential of a supramolecular approach to extend the lifetime of the chargeseparated state in photocatalytic complexes. The observed vibrational frequency shifts provide a very sensitive probe of the delocalization of the electron-spin density over the different parts of the Fe2S2 complex. The TR and spectro-electrochemical IR spectra, electron paramagnetic resonance spectra, and density functional theory calculations all show that the spin density in 3•− is delocalized over the diiron core and the NMI bridge. This delocalization explains why the complex exhibits low catalytic dihydrogen production even though it features a very efficient photoinduced electron transfer. The ultrafast porphyrin-to-NMIS2−Fe2(CO)6 photoinduced electron transfer is the first reported example of a supramolecular Fe2S2-hydrogenase model studied by femtosecond TRIR spectroscopy. Our results show that TRIR spectroscopy is a powerful tool to investigate photoinduced electron transfer in potential dihydrogen-producing catalytic complexes, and that way to optimize their performance by rational approaches.

Deficits in agency in schizophrenia, and additional deficits in body image, body schema, and internal timing, in passivity symptoms

Individuals with schizophrenia, particularly those with passivity symptoms, may not feel in control of their actions, believing them to be controlled by external agents. Cognitive operations that contribute to these symptoms may include abnormal processing in agency as well as body representations that deal with body schema and body image. However, these operations in schizophrenia are not fully understood, and the questions of general versus specific deficits in individuals with different symptom profiles remain unanswered. Using the projected-hand illusion (a digital video version of the rubber-hand illusion) with synchronous and asynchronous stroking (500 ms delay), and a hand laterality judgment task, we assessed sense of agency, body image, and body schema in 53 people with clinically stable schizophrenia (with a current, past, and no history of passivity symptoms) and 48 healthy controls. The results revealed a stable trait in schizophrenia with no difference between clinical subgroups (sense of agency) and some quantitative (specific) differences depending on the passivity symptom profile (body image and body schema). Specifically, a reduced sense of self-agency was a common feature of all clinical subgroups. However, subgroup comparisons showed that individuals with passivity symptoms (both current and past) had significantly greater deficits on tasks assessing body image and body schema, relative to the other groups. In addition, patients with current passivity symptoms failed to demonstrate the normal reduction in body illusion typically seen with a 500 ms delay in visual feedback (asynchronous condition), suggesting internal timing problems. Altogether, the results underscore self-abnormalities in schizophrenia, provide evidence for both trait abnormalities and state changes specific to passivity symptoms, and point to a role for internal timing deficits as a mechanistic explanation for external cues becoming a possible source of self-body input.

Privatisation and cross-border electricity trade: from internal market to European Supergrid?

he perspective European Supergrid would consist of an integrated power system network, where electricity demands from one country could be met by generation from another country. This paper makes use of a bi-linear fixed-effects model to analyse the determinants for trading electricity across borders among 34 countries connected by the European Supergrid. The key question that this paper aims to address is the extent to which the privatisation of European electricity markets has brought about higher cross-border trade of electricity. The analysis makes use of distance, price ratios, gate closure times, size of peaks and aggregate demand as standard determinants. Controlling for other standard determinants, it is concluded that privatisation in most cases led to higher power exchange and that the benefits are more significant where privatisation measures have been in place for a longer period.

Internal equity financing and the performance of multinational subsidiaries in emerging economies

We examine the internal equity financing of the multinational subsidiary which retains and reinvests its own earnings. Internal equity financing is a type of firm-specific advantage (FSA) along with other traditional FSAs in innovation, research and development, brands and management skills. It also reflects subsidiary-level financial management decision-making. Here we test the contributions of internal equity financing and subsidiary-level financial management decision-making to subsidiary performance, using original survey data from British multinational subsidiaries in six emerging countries in the South East Asia region. Our first finding is that internal equity financing acts as an FSA to improve subsidiary performance. Our second finding is that over 90% of financing sources (including capital investment by the parent firms) in the British subsidiaries come from internal funding. Our third finding is that subsidiary-level financial management decision-making has a statistically significant positive impact on subsidiary performance. Our findings advance the theoretical, empirical and managerial analysis of subsidiary performance in emerging economies.

Equipped to deal with uncertainty in climate and impacts predictions: lessons from internal peer review

The quantification of uncertainty is an increasingly popular topic, with clear importance for climate change policy. However, uncertainty assessments are open to a range of interpretations, each of which may lead to a different policy recommendation. In the EQUIP project researchers from the UK climate modelling, statistical modelling, and impacts communities worked together on ‘end-to-end’ uncertainty assessments of climate change and its impacts. Here, we use an experiment in peer review amongst project members to assess variation in the assessment of uncertainties between EQUIP researchers. We find overall agreement on key sources of uncertainty but a large variation in the assessment of the methods used for uncertainty assessment. Results show that communication aimed at specialists makes the methods used harder to assess. There is also evidence of individual bias, which is partially attributable to disciplinary backgrounds. However, varying views on the methods used to quantify uncertainty did not preclude consensus on the consequential results produced using those methods. Based on our analysis, we make recommendations for developing and presenting statements on climate and its impacts. These include the use of a common uncertainty reporting format in order to make assumptions clear; presentation of results in terms of processes and trade-offs rather than only numerical ranges; and reporting multiple assessments of uncertainty in order to elucidate a more complete picture of impacts and their uncertainties. This in turn implies research should be done by teams of people with a range of backgrounds and time for interaction and discussion, with fewer but more comprehensive outputs in which the range of opinions is recorded.