Application of density functional theory to analysis of energetic heterogeneity and pore size distribution of activated carbons

A new approach based on the nonlocal density functional theory to determine pore size distribution (PSD) of activated carbons and energetic heterogeneity of the pore wall is proposed. The energetic heterogeneity is modeled with an energy distribution function (EDF), describing the distribution of solid-fluid potential well depth (this distribution is a Dirac delta function for an energetic homogeneous surface). The approach allows simultaneous determining of the PSD (assuming slit shape) and EDF from nitrogen or argon isotherms at their respective boiling points by using a set of local isotherms calculated for a range of pore widths and solid-fluid potential well depths. It is found that the structure of the pore wall surface significantly differs from that of graphitized carbon black. This could be attributed to defects in the crystalline structure of the surface, active oxide centers, finite size of the pore walls (in either wall thickness or pore length), and so forth. Those factors depend on the precursor and the process of carbonization and activation and hence provide a fingerprint for each adsorbent. The approach allows very accurate correlation of the experimental adsorption isotherm and leads to PSDs that are simpler and more realistic than those obtained with the original nonlocal density functional theory.

Genetic resource impacts of habitat loss and degradation; reconciling empirical evidence and predicted theory for neotropical trees

The theoretical impacts of anthropogenic habitat degradation on genetic resources have been well articulated. Here we use a simulation approach to assess the magnitude of expected genetic change, and review 31 studies of 23 neotropical tree species to assess whether empirical case studies conform to theory. Major differences in the sensitivity of measures to detect the genetic health of degraded populations were obvious. Most studies employing genetic diversity (nine out of 13) found no significant consequences, yet most that assessed progeny inbreeding (six out of eight), reproductive output (seven out of 10) and fitness (all six) highlighted significant impacts. These observations are in line with theory, where inbreeding is observed immediately following impact, but genetic diversity is lost slowly over subsequent generations, which for trees may take decades. Studies also highlight the ecological, not just genetic, consequences of habitat degradation that can cause reduced seed set and progeny fitness. Unexpectedly, two studies examining pollen flow using paternity analysis highlight an extensive network of gene flow at smaller spatial scales (less than 10 km). Gene flow can thus mitigate against loss of genetic diversity and assist in long-term population viability, even in degraded landscapes. Unfortunately, the surveyed studies were too few and heterogeneous to examine concepts of population size thresholds and genetic resilience in relation to life history. Future suggested research priorities include undertaking integrated studies on a range of species in the same landscapes; better documentation of the extent and duration of impact; and most importantly, combining neutral marker, pollination dynamics, ecological consequences, and progeny fitness assessment within single studies.

Theory of strongly correlated electron systems. I. Intersite coulomb interaction and the approximation of renormalized fermions in total energy calculations

The diagrammatic strong-coupling perturbation theory (SCPT) for correlated electron systems is developed for intersite Coulomb interaction and for a nonorthogonal basis set. The construction is based on iterations of exact closed equations for many - electron Green functions (GFs) for Hubbard operators in terms of functional derivatives with respect to external sources. The graphs, which do not contain the contributions from the fluctuations of the local population numbers of the ion states, play a special role: a one-to-one correspondence is found between the subset of such graphs for the many - electron GFs and the complete set of Feynman graphs of weak-coupling perturbation theory (WCPT) for single-electron GFs. This fact is used for formulation of the approximation of renormalized Fermions (ARF) in which the many-electron quasi-particles behave analogously to normal Fermions. Then, by analyzing: (a) Sham's equation, which connects the self-energy and the exchange- correlation potential in density functional theory (DFT); and (b) the Galitskii and Migdal expressions for the total energy, written within WCPT and within ARF SCPT, a way we suggest a method to improve the description of the systems with correlated electrons within the local density approximation (LDA) to DFT. The formulation, in terms of renormalized Fermions LIDA (RF LDA), is obtained by introducing the spectral weights of the many electron GFs into the definitions of the charge density, the overlap matrices, effective mixing and hopping matrix elements, into existing electronic structure codes, whereas the weights themselves have to be found from an additional set of equations. Compared with LDA+U and self-interaction correction (SIC) methods, RF LDA has the advantage of taking into account the transfer of spectral weights, and, when formulated in terms of GFs, also allows for consideration of excitations and nonzero temperature. Going beyond the ARF SCPT, as well as RF LIDA, and taking into account the fluctuations of ion population numbers would require writing completely new codes for ab initio calculations. The application of RF LDA for ab initio band structure calculations for rare earth metals is presented in part 11 of this study (this issue). (c) 2005 Wiley Periodicals, Inc.

Using continuous measurement to protect a universal set of quantum gates within a perturbed decoherence-free subspace

We consider a universal set of quantum gates encoded within a perturbed decoherence-free subspace of four physical qubits. Using second-order perturbation theory and a measuring device modelled by an infinite set of harmonic oscillators, simply coupled to the system, we show that continuous observation of the coupling agent induces inhibition of the decoherence due to spurious perturbations. We thus advance the idea of protecting or even creating a decoherence-free subspace for processing quantum information.

Pore size distribution analysis of activated carbons: Application of density functional theory using nongraphitized carbon black as a reference system

The application of nonlocal density functional theory (NLDFT) to determine pore size distribution (PSD) of activated carbons using a nongraphitized carbon black, instead of graphitized thermal carbon black, as a reference system is explored. We show that in this case nitrogen and argon adsorption isotherms in activated carbons are precisely correlated by the theory, and such an excellent correlation would never be possible if the pore wall surface was assumed to be identical to that of graphitized carbon black. It suggests that pore wall surfaces of activated carbon are closer to that of amorphous solids because of defects of crystalline lattice, finite pore length, and the presence of active centers.. etc. Application of the NLDFT adapted to amorphous solids resulted in quantitative description of N-2 and Ar adsorption isotherms on nongraphitized carbon black BP280 at their respective boiling points. In the present paper we determined solid-fluid potentials from experimental adsorption isotherms on nongraphitized carbon black and subsequently used those potentials to model adsorption in slit pores and generate a corresponding set of local isotherms, which we used to determine the PSD functions of different activated carbons. (c) 2005 Elsevier Ltd. All rights reserved.

Telling the story of theory of mind: Deaf and hearing children's narratives and mental state understanding

Theory of mind (ToM) was examined in late-signing deaf children in two studies by using standard tests and measures of spontaneous talk about inner states of perception, affect and cognition during storytelling. In Study 1, there were 21 deaf children aged 6 to 11 years and 13 typical-hearing children matched with the deaf by chronological age. In Study 2, there were 17 deaf children aged 6 to 12 years and 17 typical-hearing preschoolers aged 4 to 5 years who were matched with the deaf by ToM test performance. In addition to replicating the consistently reported finding of poor performance on standard false belief tests by late-signing deaf children, significant correlations emerged in both studies between deaf children's ToM test scores and their spontaneous narrative talk about imaginative cognition (e.g. 'pretend'). In Study 2, with a new set of purpose-built pictures that evoked richer and more complex mentalistic narration than the published picture book of Study 1, results of multiple regression analyses showed that children's narrative talk about imaginative cognition was uniquely important, over and above hearing status and talking of other kinds of mental states, in predicting ToM scores. The same was true of children's elaborated narrative talk using utterances that either spelt out thoughts, explained inner states or introduced contrastives. In addition, results of a Guttman scalograrn analysis in Study 2 suggested a consistent sequence in narrative and standard test performance by deaf and hearing children that went from (1) narrative mention of visible (affective or perceptual) mental states only, along with FB failure, to (2) narrative mention of cognitive states along with (1), to (3) elaborated narrative talk about inner states along with (2), and finally to (4) simple and elaborated narrative talk about affective/perceptual and cognitive states along with FIB test success. Possible explanations for this performance ordering, as well as for the observed correlations in both studies between ToM test scores and narrative variables, were considered.

The role of self-efficacy in predicting rule-following behaviors in shelters for homeless youth: A test of the theory of planned behavior

Through a prospective study of 70 youths staying at homeless-youth shelters, the authors tested the utility of I. Ajzen's (1991) theory of planned behavior (TPB), by comparing the constructs of self-efficacy with perceived behavioral control (PBC), in predicting people's rule-following behavior during shelter stays. They performed the 1st wave of data collection through a questionnaire assessing the standard TPB components of attitudes, subjective norms, PBC, and behavioral intentions in relation to following the set rules at youth shelters. Further, they distinguished between items assessing PBC (or perceived control) and those reflecting self-efficacy (or perceived difficulty). At the completion of each youth's stay at the shelter, shelter staff rated the rule adherence for that participant. Regression analyses revealed some support for the TPB in that subjective norm was a significant predictor of intentions. However, self-efficacy emerged as the strongest predictor of intentions and was the only significant predictor of rule-following behavior. Thus, the results of the present study indicate the possibility that self-efficacy is integral to predicting rule adherence within this context and reaffirm the importance of incorporating notions of people's perceived ease or difficulty in performing actions in models of attitude-behavior prediction.

Bridging the divide between theory and practice. Experiential learning approaches for tourism and hospitality education

Experiential learning approaches such as role-play have been found to be valuable methods of bridging the divide between academic knowledge and practical skills, a problem often cited in tourism and hospitality management education. Such approaches have been found to contribute towards deeper learning by enhancing students' interest, motivation, participation, knowledge and skill development. This paper reports on the implementation of an experiential learning approach designed to encourage and facilitate deeper learning approaches, with the contributing aims of providing students with a more interesting learning experience and a broader set of skills for future employment.

The theory of on-line learning: a statistical physics approach

In this paper we review recent theoretical approaches for analysing the dynamics of on-line learning in multilayer neural networks using methods adopted from statistical physics. The analysis is based on monitoring a set of macroscopic variables from which the generalisation error can be calculated. A closed set of dynamical equations for the macroscopic variables is derived analytically and solved numerically. The theoretical framework is then employed for defining optimal learning parameters and for analysing the incorporation of second order information into the learning process using natural gradient descent and matrix-momentum based methods. We will also briefly explain an extension of the original framework for analysing the case where training examples are sampled with repetition.

Statistical mechanics of typical set decoding

The performance of "typical set (pairs) decoding" for ensembles of Gallager's linear code is investigated using statistical physics. In this decoding method, errors occur, either when the information transmission is corrupted by atypical noise, or when multiple typical sequences satisfy the parity check equation as provided by the received corrupted codeword. We show that the average error rate for the second type of error over a given code ensemble can be accurately evaluated using the replica method, including the sensitivity to message length. Our approach generally improves the existing analysis known in the information theory community, which was recently reintroduced in IEEE Trans. Inf. Theory 45, 399 (1999), and is believed to be the most accurate to date. © 2002 The American Physical Society.

Nickel(II) complexes of whole set of the simple ethylenediaminetetracarboxylate ligands:DFT study of complexes invoking molecular orbital and configurational analysis

The whole set of the nickel(II) complexes with no derivatized edta-type hexadentate ligands has been investigated from their structural and electronic properties. Two more complexes have been prepared in order to complete the whole set: trans(O5)-[Ni(ED3AP)]2- and trans(O5O6)-[Ni(EDA3P)]2- complexes. trans(O5) geometry has been verified crystallographically and trans(O5O6) geometry of the second complex has been predicted by the DFT theory and spectral analysis. Mutual dependance has been established between: the number of the five-membered carboxylate rings, octahedral/tetrahedral deviation of metal-ligand/nitrogen-neighbour-atom angles and charge-transfer energies (CTE) calculated by the Morokuma’s energetic decomposition analysis; energy of the absorption bands and HOMO–LUMO gap.

What does endogenous growth theory tell about regional economies? Empirics of R&D worker-based productivity growth

What does endogenous growth theory tell about regional economies? Empirics of R&D worker-based productivity growth, Regional Studies. Endogenous growth theory emerged in the 1990s as ‘new growth theory’ accounting for technical progress in the growth process. This paper examines the role of research and development (R&D) workers underlying the Romer model (1990) and its subsequent modifications, and compares it with a model based on the accumulation of human capital engaged in R&D. Cross-section estimates of the models against productivity growth of European regions in the 1990s suggest that each R&D worker has a unique set of knowledge while his/her contributions are enhanced by knowledge sharing within a region as well as spillovers from other regions in proximity.

On the opportunism-independent theory of the firm

Previous developments in the opportunism-independent theory of the firm are either restricted to special cases or are derived from the capabilities or resource-based perspective. However, a more general opportunism-independent approach can be developed, based on the work of Demsetz and Coase, which is nevertheless contractual in nature. This depends on 'direction', that is, deriving economic value by permitting one set of actors to direct the activities of another, and of non-human factors of production. Direction helps to explain not only firm boundaries and organisation, but also the existence of firms, without appealing to opportunism or moral hazard. The paper also considers the extent to which it is meaningful to speak of 'contractual' theories in the absence of opportunism, and whether this analysis can be extended beyond the employment contract to encompass ownership of assets by the firm. © The Author 2005. Published by Oxford University Press on behalf of the Cambridge Political Economy Society. All rights reserved.

The theory-practice divide:thoughts from the Editors and Senior Advisory Board of EJM

Purpose – The purpose of this editorial is to bring together thoughts and opinions from the Editors and Senior Advisory Board of EJM regarding the nature of the long-debated “theory-practice divide” in marketing scholarship. Design/methodology/approach – The authors synthesise diverse opinions from senior academics in order both to inspire further debate in marketing scholarship, and to draw some important conclusions for marketing academia as a whole. Findings – The authors propose that, for marketing scholarship to mature and progress, room must be found for those who wish to focus both on practical and on pure marketing scholarship. Career advancement from both routes is vital. Research limitations/implications – The topic of the theory-practice gap is complex. Many diverse opinions are cited and, due to space constraints, the coverage of many issues is necessarily brief. Practical implications – Scholars should find the thoughts contained in the paper of significant interest. Originality/value – The paper appears to be the first to bring together such a set of diverse opinions on the subject, and to try to draw some overall pragmatic conclusions, while still recognising the multiplicity of valid thought in the area.

Beyond theory:an examination of lean new product introduction practices in the UK

Interest is growing around the application of lean techniques to new product introduction (NPI). Although a relatively emergent topic compared with the application of ‘lean’ within the factory, since 2000 there has been an exponential rise in the literature on this subject. However, much of this work focuses on describing and extolling the virtues of the ‘Toyota approach’ to design. Therefore, by way of a stock take for the UK, the present authors' research has set out to understand how well lean product design practices have been adopted by leading manufacturers. This has been achieved by carrying out in-depth case studies with three carefully selected manufacturers of complex engineered products. This paper describes these studies, the detailed results and subsequent findings, and concludes that both the awareness and adoption of practices is generally embryonic and far removed from the theory advocated in the literature.