Impedance field and transition from thermal to shot noise in Cd1-xZnxTe semi-insulating Ohmic detectors

Within a drift-diffusion model we investigate the role of the self-consistent electric field in determining the impedance field of a macroscopic Ohmic (linear) resistor made by a compensated semi-insulating semiconductor at arbitrary values of the applied voltage. The presence of long-range Coulomb correlations is found to be responsible for a reshaping of the spatial profile of the impedance field. This reshaping gives a null contribution to the macroscopic impedance but modifies essentially the transition from thermal to shot noise of a macroscopic linear resistor. Theoretical calculations explain a set of noise experiments carried out in semi-insulating CdZnTe detectors.

Harmonic force fields from scaled SCF calculations: Program ASYM40

We report an extended version of our normal coordinate program ASYM40, which may be used to transform Cartesian force constants from ab initio calculations to a force field in nonredundant internal (symmetry) coordinates. When experimental data are available, scale factors for the theoretical force field may then be optimized by least-squares refinement. The alternative of refining an empirical force field to fit a wide variety of data, as with the previous version ASYM20, has been retained. We compare the results of least-squares refinement of the full harmonic force field with least-squares refinement of only the scale factors for an SCF calculated force field and conclude that the latter approach may be useful for large molecules where more sophisticated calculations are impractical. The refinement of scale factors for a theoretical force field is also useful when there are only limited spectroscopic data. The program will accept ab initio calculated force fields from any program that presents Cartesian force constants as output. The program is available through Quantum Chemistry Program Exchange.

Evaluation of data for atmospheric models: master equation/RRKM calculations on the combination reaction, BrO+NO2 -> BrONO2, a conundrum

Experimental data for the title reaction were modeled using master equation (ME)/RRKM methods based on the Multiwell suite of programs. The starting point for the exercise was the empirical fitting provided by the NASA (Sander, S. P.; Finlayson-Pitts, B. J.; Friedl, R. R.; Golden, D. M.; Huie, R. E.; Kolb, C. E.; Kurylo, M. J.; Molina, M. J.; Moortgat, G. K.; Orkin, V. L.; Ravishankara, A. R. Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies, Evaluation Number 15; Jet Propulsion Laboratory: Pasadena, California, 2006)(1) and IUPAC (Atkinson, R.; Baulch, D. L.; Cox, R. A.: R. F. Hampson, J.; Kerr, J. A.; Rossi, M. J.; Troe, J. J. Phys. Chem. Ref. Data. 2000, 29, 167) 2 data evaluation panels, which represents the data in the experimental pressure ranges rather well. Despite the availability of quite reliable parameters for these calculations (molecular vibrational frequencies (Parthiban, S.; Lee, T. J. J. Chem. Phys. 2000, 113, 145)3 and a. value (Orlando, J. J.; Tyndall, G. S. J. Phys. Chem. 1996, 100,. 19398)4 of the bond dissociation energy, D-298(BrO-NO2) = 118 kJ mol(-1), corresponding to Delta H-0(circle) = 114.3 kJ mol(-1) at 0 K) and the use of RRKM/ME methods, fitting calculations to the reported data or the empirical equations was anything but straightforward. Using these molecular parameters resulted in a discrepancy between the calculations and the database of rate constants of a factor of ca. 4 at, or close to, the low-pressure limit. Agreement between calculation and experiment could be achieved in two ways, either by increasing Delta H-0(circle) to an unrealistically high value (149.3 kJ mol(-1)) or by increasing , the average energy transferred in a downward collision, to an unusually large value (> 5000 cm(-1)). The discrepancy could also be reduced by making all overall rotations fully active. The system was relatively insensitive to changing the moments of inertia in the transition state to increase the centrifugal effect. The possibility of involvement of BrOONO was tested and cannot account for the difficulties of fitting the data.

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.

Climate model calculations of the impact of aerosols from road transport and shipping

Road transport and shipping are copious sources of aerosols, which exert a 9 significant radiative forcing, compared to, for example, the CO2 emitted by these sectors. An 10 advanced atmospheric general circulation model, coupled to a mixed-layer ocean, is used to 11 calculate the climate response to the direct radiative forcing from such aerosols. The cases 12 considered include imposed distributions of black carbon and sulphate aerosols from road 13 transport, and sulphate aerosols from shipping; these are compared to the climate response 14 due to CO2 increases. The difficulties in calculating the climate response due to small 15 forcings are discussed, as the actual forcings have to be scaled by large amounts to enable a 16 climate response to be easily detected. Despite the much greater geographical inhomogeneity 17 in the sulphate forcing, the patterns of zonal and annual-mean surface temperature response 18 (although opposite in sign) closely resembles that resulting from homogeneous changes in 19 CO2. The surface temperature response to black carbon aerosols from road transport is shown 20 to be notably non-linear in scaling applied, probably due to the semi-direct response of clouds 21 to these aerosols. For the aerosol forcings considered here, the most widespread method of 22 calculating radiative forcing significantly overestimates their effect, relative to CO2, 23 compared to surface temperature changes calculated using the climate model.

Wave-activity conservation laws and stability theorems for semi-geostrophic dynamics: part 1. pseudomomentum-based theory

There exists a well-developed body of theory based on quasi-geostrophic (QG) dynamics that is central to our present understanding of large-scale atmospheric and oceanic dynamics. An important question is the extent to which this body of theory may generalize to more accurate dynamical models. As a first step in this process, we here generalize a set of theoretical results, concerning the evolution of disturbances to prescribed basic states, to semi-geostrophic (SG) dynamics. SG dynamics, like QG dynamics, is a Hamiltonian balanced model whose evolution is described by the material conservation of potential vorticity, together with an invertibility principle relating the potential vorticity to the advecting fields. SG dynamics has features that make it a good prototype for balanced models that are more accurate than QG dynamics. In the first part of this two-part study, we derive a pseudomomentum invariant for the SG equations, and use it to obtain: (i) linear and nonlinear generalized Charney–Stern theorems for disturbances to parallel flows; (ii) a finite-amplitude local conservation law for the invariant, obeying the group-velocity property in the WKB limit; and (iii) a wave-mean-flow interaction theorem consisting of generalized Eliassen–Palm flux diagnostics, an elliptic equation for the stream-function tendency, and a non-acceleration theorem. All these results are analogous to their QG forms. The pseudomomentum invariant – a conserved second-order disturbance quantity that is associated with zonal symmetry – is constructed using a variational principle in a similar manner to the QG calculations. Such an approach is possible when the equations of motion under the geostrophic momentum approximation are transformed to isentropic and geostrophic coordinates, in which the ageostrophic advection terms are no longer explicit. Symmetry-related wave-activity invariants such as the pseudomomentum then arise naturally from the Hamiltonian structure of the SG equations. We avoid use of the so-called ‘massless layer’ approach to the modelling of isentropic gradients at the lower boundary, preferring instead to incorporate explicitly those boundary contributions into the wave-activity and stability results. This makes the analogy with QG dynamics most transparent. This paper treats the f-plane Boussinesq form of SG dynamics, and its recent extension to β-plane, compressible flow by Magnusdottir & Schubert. In the limit of small Rossby number, the results reduce to their respective QG forms. Novel features particular to SG dynamics include apparently unnoticed lateral boundary stability criteria in (i), and the necessity of including additional zonal-mean eddy correlation terms besides the zonal-mean potential vorticity fluxes in the wave-mean-flow balance in (iii). In the companion paper, wave-activity conservation laws and stability theorems based on the SG form of the pseudoenergy are presented.

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.

Empirical analysis of the Lieb-Oxford bound in ions and molecules

Universal properties of the Coulomb interaction energy apply to all many-electron systems. Bounds on the exchange-correlation energy, in particular, are important for the construction of improved density functionals. Here we investigate one such universal property-the Lieb-Oxford lower bound-for ionic and molecular systems. In recent work [J Chem Phys 127, 054106 (2007)], we observed that for atoms and electron liquids this bound may be substantially tightened. Calculations for a few ions and molecules suggested the same tendency, but were not conclusive due to the small number of systems considered. Here we extend that analysis to many different families of ions and molecules, and find that for these, too, the bound can be empirically tightened by a similar margin as for atoms and electron liquids. Tightening the Lieb-Oxford bound will have consequences for the performance of various approximate exchange-correlation functionals. (C) 2008 Wiley Periodicals Inc.

Absolute configuration reassignment of two chromanes from Peperomia obtusifolia (Piperaceae) using VCD and DFT calculations

Previous analysis of the ECD spectra of two prenylated benzopyrans isolated from Peperomia obtusifolia, by means of the helicity rule for the chromane chromophore, resulted in the incorrect assignment of their absolute configuration, (5) instead of (R) for a deduced P-helicity of the chromane ring for the (+)-enantiomers. This was discovered by the application of DFT calculations and VCD spectroscopy. Experimental and calculated (B3LYP/6-31G(d)) VCD and IR spectra were compared, and a definitive absolute configuration of (+)-1 and (+)-2 is reassigned directly in solution as (R). The assumption of equatorial positioning of bulky groups, shown here to be invalid for the title molecules, is the underlying cause of the previous incorrect assignment of absolute configuration. Moreover, TDDFT (B3LYP/6-311++G(2d,2p)//B3LYP/6-31G(d)) calculations of ECD spectra have shown that both P- and M-helicity of the heterocyclic ring, for a given absolute configuration, lead to the same sign for the (1)L(b) ECD band, thus bringing into question the validity of the empirical ECD helicity rule for chromane molecules. (C) 2010 Elsevier Ltd. All rights reserved.

A (semi-)parametric functional coefficient autoregressive conditional duration model

In this paper, we propose a class of ACD-type models that accommodates overdispersion, intermittent dynamics, multiple regimes, and sign and size asymmetries in financial durations. In particular, our functional coefficient autoregressive conditional duration (FC-ACD) model relies on a smooth-transition autoregressive specification. The motivation lies on the fact that the latter yields a universal approximation if one lets the number of regimes grows without bound. After establishing that the sufficient conditions for strict stationarity do not exclude explosive regimes, we address model identifiability as well as the existence, consistency, and asymptotic normality of the quasi-maximum likelihood (QML) estimator for the FC-ACD model with a fixed number of regimes. In addition, we also discuss how to consistently estimate using a sieve approach a semiparametric variant of the FC-ACD model that takes the number of regimes to infinity. An empirical illustration indicates that our functional coefficient model is flexible enough to model IBM price durations.

Investigação dos processos hidrossedimentológicos em parcela experimental no semi-árido potiguar

In northeastern semiarid, seasonality on precipitation temporal distribution, high intensity storm events and inadequate management of native vegetation can promote soil erosion. Vegetation removal causes soil surface exposure, reduces soil water storage capacity and can be the source degradation processes. In this context, this approach aims to analyze water and soil erosion processes on a 250 m2 undisturbed experimental plot with native vegetation, slope 2.5% by using 2006 and 2007 monitoring data. The site was instrumented to monitor rainfall, overland flow runoff and erosion by using a 5 m³ tank downstream the plot. Soil erosion monitoring was made by transported sediment and organic matter collection after each event. Field infiltration experiments were made at 16 points randomly distributed within the plot area by using a constant head infiltrometer during drought and rainy seasons, respectively. Infiltration data revealed high spatial and temporal variability. It was observed that during the beginning of the rainy period, 77% of the events showed runoff coefficient less than 0.05. As the rainy season began, soil water increase produced annual species germination. High intensity storms resulted in runoff coefficients varying between 0.33 and 0.42. Once the annual species was established, it was observed that approximately 39% of the events produced no runoff, which reflects an increase on soil water retention capacity caused by the vegetation. A gradual runoff reduction during the rainy season emphasizes the effect of vegetative density increase. Soil erosion observed data allowed to fit an empirical relationship involving soil loss and precipitation height, which was used to analyze the plot installation impact on soil erosion. Observed soil loss in 2006 and 2007 was 230 Kg/ha and 54 Kg/ha, respectively

Democratização do acesso a água no semi-árido: o caso da comunidade rural de Pendências dos Emídios no município de Serrinha/RN

Brazil lives a time of experimentation and maturity as it pertains to managing the use of water, which comes institutionalising increasingly social participation. In Rio Grande do Norte, since 1997, the government has been developing actions accordingly, through the State Department of Water Resources, which has implemented a programme of adutoras within the State and created Water Users Associations, in the installation of dessalinizadores for places where the Adutora was not necessary or not yet arrived, so that should be managed by communities through associations of users. Since 2003, Civil Society Organisations - CSOs come through ASA - Articulation in the Semi-arid Brazilian, implementing the P1MC - Program of Training and Mobilization for Social Living with the Semi-Arid (One Million Rural Cisternas), in its third year of implementation in Rio Grande do Norte, in the spirit of working together with the semi arid. In the municipality of Serrinha / RN which incorporates the Semi-arid region, we find in the rural community of Pendêcias dos Emídios the experience of the State and Civil Society, which referred to a discussion about the environmental sustainability of these initiatives. The general objective of this work is to examine the strategies for participatory management in the use and access to water in the community of Pendêcias dos Emídios of the municipality of Serrinha / RN, to understand how those experiences can contribute to environmental sustainability. The methodology used envolvel bibliographic research in categories involving each article, the analysis of the terms of reference of each strategy as part of the documentary research, the application forms covering 40 families benefited, and interviews based on comprehensive analysis of the speech. This study is divided into 02 articles, where the first is a discussion held on collective action and environmental sustainability, and the second is held a discussion about the sustainability of the initiatives underway to access water. The results of the discussion held on 02 articles that had their empirical built from the experience of the Commonwealth of Pendências dos Emídios revealed how far will the ability of the State to promote collective action and the limitations of the perception of sustainability that permeates these initiatives in the search for democratic access to water in semi-arid

Absolute configuration reassignment of two chromanes from Peperomia obtusifolia (Piperaceae) using VCD and DFT calculations

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

A cultura ribeirinha entre o saber local e o saber global numa visão etnomatemática

Esta dissertação é o resultado de uma pesquisa que teve como objetivo analisar como um grupo de ribeirinhos, moradores da ilha João Pilatos (Ananindeua - PA), relaciona os conhecimentos ministrados no curso de formação para empreendedores rurais com os conhecimentos que possui da tradição ribeirinha e, em especial, os conhecimentos matemáticos. A parte empírica dessa pesquisa aconteceu em dois lugares e em momentos diferentes: o primeiro deles ocorreu na ilha João Pilatos, onde foram coletadas informações sobre o histórico das comunidades existentes na ilha, sobre os afazeres do cotidiano e sobre as práticas de pesca, de plantio, de coleta na floresta, de preparação do carvão e sobre a comercialização desses produtos. Nesse momento, os únicos recursos utilizados foram caderno e caneta para anotações e a técnica da escuta e do diálogo. O segundo momento ocorreu no curso de formação para empreendedores rurais ministrado pelo SENAR (Serviço Nacional de Aprendizagem Rural). Nesse local, minha participação no grupo estava restrita a escutar e olhar os gestos e expressões faciais de todos os presentes. Em função disso, a observação seguida de anotações foram as técnicas utilizadas durante esse período. Após o curso, foram realizadas entrevistas semi-estruturadas com os sujeitos dessa pesquisa com o objetivo de complementar as anotações feitas durante o curso. A Sociologia e a Etnomatemática foram as bases teóricas utilizadas na organização e análise das informações de campo. No campo da sociologia, busquei Antony Giddens, Renato Ortiz e Georges Balandier para analisar o fenômeno da globalização econômica e social sobre a cultura ribeirinha e Berger & Luckmann com a sua teoria "A construção social da realidade" para analisar o cotidiano e a produção de conhecimento na vida cotidiana. No campo da Etnomatemática, utilizei a Etnomatemática numa abordagem D'Ambrosiana e as pesquisas da área. Ao final das análises, no que diz respeito à matemática, percebi que ter domínio sobre os cálculos e fórmulas dessa área do conhecimento não era condição suficiente para que os sujeitos da pesquisa alcançassem o objetivo do curso, uma vez que tanto para os empreendedores quanto para os ribeirinhos a matemática era uma forma de ver e explicar o mundo que tinha significados específicos de cada contexto. A partir desse conflito cultural, é possível indicar que os sujeitos da pesquisa atingiriam o objetivo do curso e estabeleceriam o maior número de relações entre a matemática escolar e os saberes da tradição se a matemática estudada, no curso, fosse ressignificada no contexto ribeirinho. Como consequência da primeira análise, também é possível concluir que, mediante a concepção atualmente existente no ambiente escolar que separa e não apenas distingue os valores culturais, que considera a produção de conhecimentos proveniente apenas de ambientes acadêmicos científicos e que esses tipos de conhecimentos devem ser socializados de forma disciplinar, as possibilidades de um maior número de relações entre os saberes da tradição cultural e da tradição científica têm mais chances de ocorrer em ambientes não escolares.