Density Functional Calculations On First-Row Transition Metals

The excitation energies and ionization potentials of the atoms in the first transition series are notoriously difficult to compute accurately. Errors in calculated excitation energies can range from 1--4 eV at the Hartree-Fock level, and errors as high as 1.5eV are encountered for ionization energies. In the current work we present and discuss the results of a systematic study of the first transition series using a spin-restricted Kohn-Sham density-functional method with the gradient-corrected functionals of Becke and Lee, Yang and Parr. Ionization energies are observed to be in good agreement with experiment, with a mean absolute error of approximately 0.15eV; these results are comparable to the most accurate calculations to date, the Quadratic Configuration Interaction (QCISD(T)) calculations of Raghavachari and Trucks. Excitation energies are calculated with a mean error of approximately 0.5eV, compared with \sim 1\mbox{eV} for the local density approximation and 0.1eV for QCISD(T). These gradient-corrected functionals appear to offer an attractive compromise between accuracy and computational effort.Comment: Journal of Chemical Physics, 29, LA-UR-93-425

A Pyrrole-Based Triazolium-Phane with Nh and Cationic Ch Donor Groups as a Receptor for Tetrahedral Oxyanions that Functions in Polar Media

The pyrrole-based triazolium-phane 1(4+)center dot 4BF(4)(-) has been prepared via the tetraalkylation of a macrocycle originally prepared via click chemistry. It displays a high selectivity for tetrahedral oxyanions relative to various test monoanions and trigonal planar anions in mixed polar organic-aqueous media. This selectivity is solvent dependent and is less pronounced in acetonitrile. Theoretical calculations were carried out in with the chloride anion in an effort to understand the influence of solvent on the intrinsic hydrogen bonding ability of the donor groups (pyrrole N-H, benzene C-H and triazolium C-H). The host-guest interactions between receptor 1(4+)center dot 4BF(4)(-) and representative tetrahedral oxyanions were further analysed by H-1 NMR spectroscopy, and the findings proved consistent with the differences in the intrinsic strength of the various H-bond donor groups inferred from the electronic structure calculations carried out in methanol, namely that (CH)(+)-anion interactions are less important in an energetic sense than neutral CH-anion interactions in polar media. Single crystal X-ray diffraction analyses of the mixed salts 1(4+)center dot HP2O73-center dot BF4- and 31(4+)center dot 4H(2)PO(4)(-)center dot 8BF(4)(-) confirmed that receptor 1(4+) can bind the pyrophosphate and phosphate anions in the solid state.Cai, Jiajia, Benjamin P. Hay, Neil J. Young, Xiaoping Yang, and Jonathan L. Sessler. "A pyrrole-based triazolium-phane with NH and cationic CH donor groups as a receptor for tetrahedral oxyanions that functions in polar media." Chemical Science 4, no. 4 (Jan., 2013): 1560-1567.Chemistr

Anti-Trust and Economic Theory: Some Observations from the US Experience

Recent developments in US anti-trust can be characterised as reflecting the uneasy interaction of two quite separate phenomena: first, the increased emphasis on economic analysis as the overriding organising principle of anti-trust policy and on economic efficiency as the primary (perhaps only) relevant goal for anti-trust; second, the long-standing reluctance of the federal judiciary to involve itself in any substantive economic analysis, and the preference, instead, for simple rules of thumb or ‘pigeon holes’ to sort out lawful from unlawful conduct. The result has been that while economics has played a major role, it has not influenced American anti-trust as thoroughly or as uniformly as might have been imagined; rather the extent and the nature of its influence have depended on the degree to which the relevant economics could be reduced to the kind of simple rules or pigeon holes that the judiciary favours. The present paper will illustrate that theme, first by reporting on the two developments separately and then by illustrating their joint influence with reference to two important areas of American anti-trust: predatory conduct and so-called vertical restraints. Finally, a contrast will be made between judicial development in those two areas and recent American merger policy which, it is argued, is carried out largely independently of the judiciary, and hence the opportunities for economics to influence the process are less inhibited by the judicial reluctance to undertake extensive economic analysis

The Drosophila Caspase DRONC Cleaves following Glutamate or Aspartate and Is Regulated by DIAP1, HID, and GRIM

The caspase family of cysteine proteases plays important roles in bringing about apoptotic cell death. All caspases studied to date cleave substrates COOH-terminal to an aspartate. Here we show that the Drosophila caspase DRONC cleaves COOH-terminal to glutamate as well as aspartate. DRONC autoprocesses itself following a glutamate residue, but processes a second caspase, drICE, following an aspartate. DRONC prefers tetrapeptide substrates in which aliphatic amino acids are present at the P2 position, and the P1 residue can be either aspartate or glutamate. Expression of a dominant negative form of DRONC blocks cell death induced by the Drosophila cell death activators reaper, hid, and grim, and DRONC overexpression in flies promotes cell death. Furthermore, the Drosophila cell death inhibitor DIAP1 inhibits DRONC activity in yeast, and DIAP1's ability to inhibit DRONC-dependent yeast cell death is suppressed by HID and GRIM. These observations suggest that DRONC acts to promote cell death. However, DRONC activity is not suppressed by the caspase inhibitor and cell death suppressor baculovirus p35. We discuss possible models for DRONC function as a cell death inhibitor

Globalization, the ambivalence of European integration and the possibilities for a post-disciplinary EU studies

Using the work of Manuel Castells as a starting point, this article explores the ambivalent relationship between globalization and European integration and the variety of ways in which the mainstream political science of the EU has attempted to deal with this issue. The analysis here suggests that various 'mainstreaming' disciplinary norms induce types of work that fail to address fully the somewhat paradoxical and counter-intuitive range of possible relationships between globalization and European integration. The article explores critically four possible analytical ways out of this paradox—abandonment of the concept of globalization, the development of definition precision in globalization studies, the reorientation of work to focus on globalization as discourse, and inter- and post-disciplinarity. The argument suggests that orthodox discussions of the relationship require a notion of social geography that sits at odds with much of the literature on globalization and while greater dialogue between disciplines is to be welcomed, a series of profound epistemological questions need to be confronted if studies of the interplay between global and social process are to be liberated from their disciplinary chains

Strength in diversity: enhancing learning in vocationally-orientated, master's level courses

Postgraduate education in geography, especially at the Master’s level, is undergoing significant changes in the developed world. There is an expansion of vocationally-oriented degree programmes, increasing recruitment of international students, integration of work place skills, and the engagement of non-traditional postgraduate students as departments respond to policies for a more ‘inclusive’ higher education. This paper sets the context by outlining some programmatic changes in selected countries (Australia, the UK, and the USA). We briefly reflect on how postgraduate ‘bars’ or ‘levels’ are defined and explore in detail what ‘diversity’ or ‘heterogeneity’ means in these new postgraduate settings. The paper then explores some examples of practice drawn from our own experiences, whilst recognising that relevance will vary in other contexts. Finally we consider how diversity can be harnessed as a strength that has potential to enhance taught elements of contemporary postgraduate education in and beyond the discipline

Paper 4 : Schooling, identity and social connectivity

This paper will report on the progress of a large three year Australian Research Council (ARC) grant awarded to a multidisciplinary team of researchers in Victoria, Australia. The research, A multi-disciplinary investigation of how trauma and chronic illness impact on schooling, identity and social connectivity commenced in 2007 and is known as Keeping Connected (2007). The research is a collaborative grant in partnership with the Royal Children&rsquo;s Hospital Education Institute, in association with the Melbourne Graduate School of Education, University of Melbourne and the Centre for Adolescent Health, Royal Children&rsquo;s Hospital. The research aims to investigate qualitatively, longitudinally and through multiple perspectives how young people construct/reconstruct identity and relationships with schooling following disruption associated with chronic illness. Using a mixed methodology, but with a central focus on longitudinal qualitative studies from the perspective of the young people, the study aims to identify key elements of disruption or continued connection, and will illuminate identity issues of people facing this disruption at different age and schooling points. The research outcomes will support education and health practices and provide a differently focused empirical contribution to the literature on education and social connection. The paper works at mixing methods qualitatively, rather than focusing on the overall mixed method design of the study. Assemblages of social capital theory and sociomateriality may be a useful standpoint for the development of our empirical contribution.<br /

Primitive Shape Imagery Classification from Electroencephalography

Introduction: Brain-computer interfaces (BCIs) augment traditional interfaces for human-computer interaction and provide alternative communication devices to enable the physically impaired to work. Imagined object/shape classification from electroencephalography (EEG) may lead, for example, to enhanced tools for fields such as engineering, design, and the visual arts. Evidence to support such a proposition from non-invasive neuroimaging techniques to date has mainly involved functional magnetic resonance tomography (fMRI) [1] indicating that visual perception and mental imagery show similar brain activity patterns [2] and, although the primary visual cortex has an important role in mental imagery and perception, the occipitotemporal cortex also encodes sensory, semantic and emotional properties during shape imagery [3]. Here we investigate if five imagined primitive shapes (sphere, cone, pyramid, cylinder, cube) can be classified from EEG using filter bank common spatial patterns (FBCSP) [4]. Material, Methods, and Results: Ten healthy volunteers (8 males and 2 females, aged 26-44) participated in a single session study (three runs, four blocks/run, 30 trials/block (i.e., six repetitions of five primitive shapes in random order)). Trials lasted 7s as shown in Fig. 1 and ended with an auditory tone. Thirty EEG channels were recorded with a g.BSamp EEG system using active electrodes (g.tec, Austria). EEG channels with high-level noise were removed. Signals were band-pass filtered in six non-overlapped, 4Hz width bands covering the 4-40Hz frequency range. Filter bank common spatial pattern (FBCSP) based feature extraction and mutual information (MI) based feature selection methods provided input features for 2-class classification using linear discriminant analysis (LDA) for target shape versus the rest, separately. The final 5-class classification was decided by assessing the signed distance in the 2-class discriminant hyperplane for each of the five binary classifiers as shown in Fig. 1. Classifiers were trained on two runs and tested on the one unseen run (i.e., 3 fold cross-validation). A Wilcoxon non-parametric test was used to validate the difference of DA at end of the resting period (-1s) and at the maximal peak accuracy occurring during the shape imagery task (0-3s) is significant (p<0.001). Fig. 1 shows the between-subject average time-varying classification accuracies with standard deviation (shaded area). Discussion: The results indicate that there is separability provided by the shape imagery and there is significantly higher accuracy compared to the ~20% chance level prior the display period with maximum accuracy reaching 34%. In [5] classification of five imagined primitive and complex shapes with 44% accuracy is reported using a 14 channel Emotiv headset. Differences in performance reported may be influenced by EEG recording (EEG in [5] appears to have different dynamics (significant mean shifts)), the study had more sessions/trials, applied ICA for noise removal and the participants had designer experience whilst our study did not. Improvement of our methods is required to achieve higher accuracy rate. It is unclear if an online feedback to shape imagery training and learning will an impact performance – a multisession online study with feedback is the next step in this research. Significance: To best of our knowledge this is only the second study of shape imagery classification from EEG