Mononuclear and binuclear ruthenium(II) complexes with 4-(phenyl) thiosemicarbazone of benzaldehyde: a discussion on the relative stabilities of the four-membered and five-membered chelate rings formed by the ligand

Three new ruthenium complexes of the formulae cis-[Ru(PPh3)(2)(BzTscbz)(2)] (1a), [Ru-2(PPh3)(2)(BzTscbz)(4)] (1b) and [Ru(PPh3)(2)(BzTscHbz)(2)](ClO4)(2) (2) [BzTscHbz = 4-(phenyl) thiosemicarbazone of benzaldehyde] have been synthesized and characterized by various physicochemical methods including X-ray structure determinations for 1a and 1b. The relative stabilities of the four-membered versus five-membered chelate rings formed by the deprotonated ligand BzTscbz are discussed on the basis of the experimental results and some semi-empirical as well as DFT calculations. (c) 2005 Elsevier Ltd. All rights reserved.

Understanding and projecting sea level change

There is intense scientific and public interest in the Intergovernmental Panel on Climate Change (IPCC) projections of sea level for the twenty-first century and beyond. The Fourth Assessment Report (AR4) projections, obtained by applying standard methods to the results of the World Climate Research Programme Coupled Model Experiment, includes estimates of ocean thermal expansion, the melting of glaciers and ice caps (G&ICs), increased melting of the Greenland Ice Sheet, and increased precipitation over Greenland and Antarctica, partially offsetting other contributions. The AR4 recognized the potential for a rapid dynamic ice sheet response but robust methods for quantifying it were not available. Illustrative scenarios suggested additional sea level rise on the order of 10 to 20 cm or more, giving a wide range in the global averaged projections of about 20 to 80 cm by 2100. Currently, sea level is rising at a rate near the upper end of these projections. Since publication of the AR4 in 2007, biases in historical ocean temperature observations have been identified and significantly reduced, resulting in improved estimates of ocean thermal expansion. Models that include all climate forcings are in good agreement with these improved observations and indicate the importance of stratospheric aerosol loadings from volcanic eruptions. Estimates of the volumes of G&ICs and their contributions to sea level rise have improved. Results from recent (but possibly incomplete) efforts to develop improved ice sheet models should be available for the 2013 IPCC projections. Improved understanding of sea level rise is paving the way for using observations to constrain projections. Understanding of the regional variations in sea level change as a result of changes in ocean properties, wind-stress patterns, and heat and freshwater inputs into the ocean is improving. Recently, estimates of sea level changes resulting from changes in Earth's gravitational field and the solid Earth response to changes in surface loading have been included in regional projections. While potentially valuable, semi-empirical models have important limitations, and their projections should be treated with caution

A high-resolution near-infrared extraterrestrial solar spectrum derived from ground-based Fourier transform spectrometer measurements

A detailed spectrally-resolved extraterrestrial solar spectrum (ESS) is important for line-by-line radiative transfer modeling in the near-infrared (near-IR). Very few observationally-based high-resolution ESS are available in this spectral region. Consequently the theoretically-calculated ESS by Kurucz has been widely adopted. We present the CAVIAR (Continuum Absorption at Visible and Infrared Wavelengths and its Atmospheric Relevance) ESS which is derived using the Langley technique applied to calibrated observations using a ground-based high-resolution Fourier transform spectrometer (FTS) in atmospheric windows from 2000–10000 cm-1 (1–5 μm). There is good agreement between the strengths and positions of solar lines between the CAVIAR and the satellite-based ACE-FTS (Atmospheric Chemistry Experiment-FTS) ESS, in the spectral region where they overlap, and good agreement with other ground-based FTS measurements in two near-IR windows. However there are significant differences in the structure between the CAVIAR ESS and spectra from semi-empirical models. In addition, we found a difference of up to 8 % in the absolute (and hence the wavelength-integrated) irradiance between the CAVIAR ESS and that of Thuillier et al., which was based on measurements from the Atmospheric Laboratory for Applications and Science satellite and other sources. In many spectral regions, this difference is significant, as the coverage factor k = 2 (or 95 % confidence limit) uncertainties in the two sets of observations do not overlap. Since the total solar irradiance is relatively well constrained, if the CAVIAR ESS is correct, then this would indicate an integrated “loss” of solar irradiance of about 30 W m-2 in the near-IR that would have to be compensated by an increase at other wavelengths.

Analysis of incoherent scatter spectra from non-Maxwellian plasma

Incoherent scatter data from non-thermal F-region ionospheric plasma are analysed, using theoretical spectra predicted by Raman et al. It is found that values of the semi-empirical drift parameter D∗, associated with deviations of the ion velocity distribution from a Maxwellian, and the plasma temperatures can be rigorously deduced (the results being independent of the path of iteration) if the angle between the line-of-sight and the geomagnetic field is larger than about 15–20 degrees. For small aspect angles, the deduced value of the average (or 3-D) ion temperature remains ambiguous and the analysis is restricted to the determination of the line-of-sight temperature because the theoretical spectrum is insensitive to non-thermal effects when the plasma is viewed along directions almost parallel to the magnetic field. This limitation is expected to apply to any realistic model of the ion velocity distribution, and its consequences are discussed. Fit strategies which allow for mixed ion composition are also considered. Examples of fits to data from various EISCAT observing programmes are presented.

Oblique h.f. radiowave propagation in the main trough region of the ionosphere

The propagation of 7.335 MHz, c.w. signals over a 5212 km sub-auroral, west-east path is studied. Measurements and semi-empirical predictions are made of the amplitude distributions and Doppler shifts of the received signals. The observed amplitude distribution is fitted with one produced by a numerical fading model, yielding the power losses suffered by the signals during propagation via the predominating modes. The signals are found to suffer exceptionally low losses at certain local times under geomagnetically quiet conditions. The mid-latitude trough in the F2 peak ionization density is predicted by a statistical model to be at the latitudes of this path at these times and at low Kp values. A sharp cut-off in low-power losses at a mean Kp of 2.75 strongly implicates the trough in the propagation of these signals. The Doppler shifts observed at these times cannot be explained by a simple ray-tracing model. It is shown however, that a simple extension of this model to allow for the trough can reproduce the form of the observed diurnal variation.

Enacting competitiveness: an empirical investigation

The paper draws from three case studies of regional construction firms operating in the UK. The case studies provide new insights into the ways in which such firms strive to remain competitive. Empirical data was derived from multiple interactions with senior personnel from with each firm. Data collection methods included semi-structured interviews, informal interactions, archival research, and workshops. The initial research question was informed by existing resource-based theories of competitiveness and an extensive review of constructionspecific literature. However, subsequent emergent empirical findings progressively pointed towards the need to mobilise alternative theoretical models that emphasise localised learning and embeddedness. The findings point towards the importance of de-centralised structures that enable multiple business units to become embedded within localised markets. A significant degree of autonomy is essential to facilitate entrepreneurial behaviour. In essence, sustained competitiveness was found to rest on the way de-centralised business units enact ongoing processes of localised learning. Once local business units have become embedded within localised markets, the essential challenge is how to encourage continued entrepreneurial behaviour while maintaining some degree of centralised control and coordination. This presents a number of tensions and challenges which play out differently across each of the three case studies.

The symbiotic roles of empirical experimentation and thought experimentation in the learning of physics

This study was an attempt to identify the epistemological roots of knowledge when students carry out hands-on experiments in physics. We found that, within the context of designing a solution to a stated problem, subjects constructed and ran thought experiments intertwined within the processes of conducting physical experiments. We show that the process of alternating between these two modes- empirically experimenting and experimenting in thought- leads towards a convergence on scientifically acceptable concepts. We call this process mutual projection. In the process of mutual projection, external representations were generated. Objects in the physical environment were represented in an imaginary world and these representations were associated with processes in the physical world. It is through this coupling that constituents of both the imaginary world and the physical world gain meaning. We further show that the external representations are rooted in sensory interaction and constitute a semi-symbolic pictorial communication system, a sort of primitive 'language', which is developed as the practical work continues. The constituents of this pictorial communication system are used in the thought experiments taking place in association with the empirical experimentation. The results of this study provide a model of physics learning during hands-on experimentation.

Constructing summary statistics for approximate Bayesian computation: semi-automatic approximate Bayesian computation

Many modern statistical applications involve inference for complex stochastic models, where it is easy to simulate from the models, but impossible to calculate likelihoods. Approximate Bayesian computation (ABC) is a method of inference for such models. It replaces calculation of the likelihood by a step which involves simulating artificial data for different parameter values, and comparing summary statistics of the simulated data with summary statistics of the observed data. Here we show how to construct appropriate summary statistics for ABC in a semi-automatic manner. We aim for summary statistics which will enable inference about certain parameters of interest to be as accurate as possible. Theoretical results show that optimal summary statistics are the posterior means of the parameters. Although these cannot be calculated analytically, we use an extra stage of simulation to estimate how the posterior means vary as a function of the data; and we then use these estimates of our summary statistics within ABC. Empirical results show that our approach is a robust method for choosing summary statistics that can result in substantially more accurate ABC analyses than the ad hoc choices of summary statistics that have been proposed in the literature. We also demonstrate advantages over two alternative methods of simulation-based inference.