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.

Landscape typology in the Mediterranean context: a tool for habitat restoration

Despite the wide use of Landscape Character Assessment (LCA) as a tool for landscape planning in NW Europe, there are few examples of its application in the Mediterranean. This paper reports on the results from the development of a typology for LCA in a study area of northern Sardinia, Italy to provide a spatial framework for the analysis of current patterns of cork oak distribution and future restoration of this habitat. Landscape units were derived from a visual interpretation of map data stored within a GIS describing the physical and cultural characteristics of the study area. The units were subsequently grouped into Landscape Types according to the similarity of shared attributes using Two Way Indicator Species Analysis (TWINSPAN). The preliminary results showed that the methodology classified distinct Landscape Types but, based on field observations, there is a need for further refinement of the classification. The distribution and properties of two main cork oak habitats types was examined within the identified Landscape Types namely woodlands and wood pastures using Patch Analyst. The results show very clearly a correspondence between the distribution of cork oak pastures and cork oak woodland and landscape types. This forms the basis of the development of strategies for the maintenance, restoration and recreation of these habitat types within the study area, ultimately for the whole island of Sardinia. Future work is required to improve the landscape characterisation , particularly with respect to cultural factors, and to determine the validity of the landscape spatial framework for the analysis of cork oak distribution as part of a programme of habitat restoration and re-creation.

Solving surface structures from normal incidence X-ray standing wave data

A program is provided to determine structural parameters of atoms in or adsorbed on surfaces by refinement of atomistic models towards experimentally determined data generated by the normal incidence X-ray standing wave (NIXSW) technique. The method employs a combination of Differential Evolution Genetic Algorithms and Steepest Descent Line Minimisations to provide a fast, reliable and user friendly tool for experimentalists to interpret complex multidimensional NIXSW data sets.

Extracting and validating force fields for disordered polymeric materials from neutron scattering data

We present a new approach that allows the determination and refinement of force field parameters for the description of disordered macromolecular systems from experimental neutron diffraction data obtained over a large Q range. The procedure is based on tight coupling between experimentally derived structure factors and computer modelling. By separating the potential into terms representing respectively bond stretching, angle bending and torsional rotation and by treating each of them separately, the various potential parameters are extracted directly from experiment. The procedure is illustrated on molten polytetrafluoroethylene.

Case study part 1: how to calculate appropriate deterministic long-term toxicity to exposure rates (TERs) for birds and mammals

In the European Union, first-tier assessment of the long-term risk to birds and mammals from pesticides is based on calculation of a deterministic long-term toxicity/exposure ratio(TERlt). The ratio is developed from generic herbivores and insectivores and applied to all species. This paper describes two case studies that implement proposed improvements to the way long-term risk is assessed. These refined methods require calculation of a TER for each of five identified phases of reproduction (phase-specific TERs) and use of adjusted No Observed Effect Levels (NOELs)to incorporate variation in species sensitivity to pesticides. They also involve progressive refinement of the exposure estimate so that it applies to particular species, rather than generic indicators, and relates spraying date to onset of reproduction. The effect of using these new methods on the assessment of risk is described. Each refinement did not necessarily alter the calculated TER value in a way that was either predictable or consistent across both case studies. However, use of adjusted NOELs always reduced TERs, and relating spraying date to onset of reproduction increased most phase-specific TERs. The case studies suggested that the current first-tier TERlt assessment may underestimate risk in some circumstances and that phase-specific assessments can help identify appropriate risk-reduction measures. The way in which deterministic phase-specific assessments can currently be implemented to enhance first-tier assessment is outlined.

Stratosphere‐troposphere coupling and annular mode variability in chemistry‐climate models

The internal variability and coupling between the stratosphere and troposphere in CCMVal‐2 chemistry‐climate models are evaluated through analysis of the annular mode patterns of variability. Computation of the annular modes in long data sets with secular trends requires refinement of the standard definition of the annular mode, and a more robust procedure that allows for slowly varying trends is established and verified. The spatial and temporal structure of the models’ annular modes is then compared with that of reanalyses. As a whole, the models capture the key features of observed intraseasonal variability, including the sharp vertical gradients in structure between stratosphere and troposphere, the asymmetries in the seasonal cycle between the Northern and Southern hemispheres, and the coupling between the polar stratospheric vortices and tropospheric midlatitude jets. It is also found that the annular mode variability changes little in time throughout simulations of the 21st century. There are, however, both common biases and significant differences in performance in the models. In the troposphere, the annular mode in models is generally too persistent, particularly in the Southern Hemisphere summer, a bias similar to that found in CMIP3 coupled climate models. In the stratosphere, the periods of peak variance and coupling with the troposphere are delayed by about a month in both hemispheres. The relationship between increased variability of the stratosphere and increased persistence in the troposphere suggests that some tropospheric biases may be related to stratospheric biases and that a well‐simulated stratosphere can improve simulation of tropospheric intraseasonal variability.

Diversifying into technical clothing manufacture as entrepreneurial learning: a situated learning theory perspective

Purpose – The purpose of this paper is to demonstrate analytically how entrepreneurial action as learning relating to diversifying into technical clothing – i.e. a high-value manufacturing sector – can take place. This is particularly relevant to recent discussion and debate in academic and policy-making circles concerning the survival of the clothing manufacture industry in developed industrialised countries. Design/methodology/approach – Using situated learning theory (SLT) as the major analytical lens, this case study examines an episode of entrepreneurial action relating to diversification into a high-value manufacturing sector. It is considered on instrumentality grounds, revealing wider tendencies in the management of knowledge and capabilities requisite for effective entrepreneurial action of this kind. Findings – Boundary events, brokers, boundary objects, membership structures and inclusive participation that addresses power asymmetries are found to be crucial organisational design elements, enabling the development of inter- and intracommunal capacities. These together constitute a dynamic learning capability, which underpins entrepreneurial action, such as diversification into high-value manufacturing sectors. Originality/value – Through a refinement of SLT in the context of entrepreneurial action, the paper contributes to an advancement of a substantive theory of managing technological knowledge and capabilities for effective diversification into high-value manufacturing sectors.

Voronoi, Delaunay, and Block-Structured Mesh Refinement for Solution of the Shallow-Water Equations on the Sphere

Alternative meshes of the sphere and adaptive mesh refinement could be immensely beneficial for weather and climate forecasts, but it is not clear how mesh refinement should be achieved. A finite-volume model that solves the shallow-water equations on any mesh of the surface of the sphere is presented. The accuracy and cost effectiveness of four quasi-uniform meshes of the sphere are compared: a cubed sphere, reduced latitude–longitude, hexagonal–icosahedral, and triangular–icosahedral. On some standard shallow-water tests, the hexagonal–icosahedral mesh performs best and the reduced latitude–longitude mesh performs well only when the flow is aligned with the mesh. The inclusion of a refined mesh over a disc-shaped region is achieved using either gradual Delaunay, gradual Voronoi, or abrupt 2:1 block-structured refinement. These refined regions can actually degrade global accuracy, presumably because of changes in wave dispersion where the mesh is highly nonuniform. However, using gradual refinement to resolve a mountain in an otherwise coarse mesh can improve accuracy for the same cost. The model prognostic variables are height and momentum collocated at cell centers, and (to remove grid-scale oscillations of the A grid) the mass flux between cells is advanced from the old momentum using the momentum equation. Quadratic and upwind biased cubic differencing methods are used as explicit corrections to a fast implicit solution that uses linear differencing.

The method of predicate least squares refinement

Parameters to be determined in a least squares refinement calculation to fit a set of observed data may sometimes usefully be `predicated' to values obtained from some independent source, such as a theoretical calculation. An algorithm for achieving this in a least squares refinement calculation is described, which leaves the operator in full control of the weight that he may wish to attach to the predicate values of the parameters.

Goal-refinement appraisal of soft projects (GRASP)

Industrial projects are often complex and burdened with time pressures and a lack of information. The term 'soft-project' used here stands for projects where the ‘what’ and/or the ‘how’ is uncertain, which is often the experience in projects involving software intensive systems developments. This thesis intertwines the disciplines of project management and requirements engineering in a goal-oriented application of the maxim ‘keep all objectives satisfied’. It thus proposes a method for appraising projects. In this method, a goal-oriented analysis establishes a framework with which expert judgements are collected so as to construct a confidence profile in regard to the feasibility and adequacy of the project's planned outputs. It is hoped that this appraisal method will contribute to the activities of project ‘shaping’ and aligning stakeholders’ expectations whilst helping project managers appreciate what parts of their project can be progressed and what parts should be held pending further analysis. This thesis offers the following original contribution: an appreciation of appraisal in the project context; a goal-oriented confidence profiling technique; and: a technique to produce goal-refinement diagrams – referred to as Goal Sketching. Collectively these amount to a method for the ‘Goal Refinement Appraisal of Soft-Projects’ (GRASP). The validity of the GRASP method is shown for two projects. In the first it is used for shaping a business investigation project. This is done in real-time in the project. The second case is a retrospective study of an enterprise IT project. This case tests the effectiveness of forecasting project difficulty from an initial confidence profile.

Visual Object Recognition Using Deformable Models of Vehicles

This workshop paper reports recent developments to a vision system for traffic interpretation which relies extensively on the use of geometrical and scene context. Firstly, a new approach to pose refinement is reported, based on forces derived from prominent image derivatives found close to an initial hypothesis. Secondly, a parameterised vehicle model is reported, able to represent different vehicle classes. This general vehicle model has been fitted to sample data, and subjected to a Principal Component Analysis to create a deformable model of common car types having 6 parameters. We show that the new pose recovery technique is also able to operate on the PCA model, to allow the structure of an initial vehicle hypothesis to be adapted to fit the prevailing context. We report initial experiments with the model, which demonstrate significant improvements to pose recovery.

High-resolution, unstructured meshes for hydrodynamic models of the Great Barrier Reef, Australia

Accuracy and mesh generation are key issues for the high-resolution hydrodynamic modelling of the whole Great Barrier Reef. Our objective is to generate suitable unstructured grids that can resolve topological and dynamical features like tidal jets and recirculation eddies in the wake of islands. A new strategy is suggested to refine the mesh in areas of interest taking into account the bathymetric field and an approximated distance to islands and reefs. Such a distance is obtained by solving an elliptic differential operator, with specific boundary conditions. Meshes produced illustrate both the validity and the efficiency of the adaptive strategy. Selection of refinement and geometrical parameters is discussed. (c) 2006 Elsevier Ltd. All rights reserved.

Normal coordinates for the planar vibrations of benzene

Force constants and normal coordinates have been recalculated for all of the in-plane vibrations of benzene, making use of the recently observed data on one of the Coriolis constants in the E2g species from the work of Callomon et al. The extent to which the force field is uniquely determined by the data is reviewed for each symmetry species in turn, and the results of a force constant refinement calculation are reported in which a modified valency force field was used based on the hybrid orbital model. The results show considerable differences from Whiffen's normal coordinates for benzene, but somewhat smaller differences from Scherer's recent calculations.

The calculation of force constants and normal co-ordinates II: methyl fluoride

The mathematical difficulties which can arise in the force constant refinement procedure for calculating force constants and normal co-ordinates are described and discussed. The method has been applied to the methyl fluoride molecule, using an electronic computer. The best values of the twelve force constants in the most general harmonic potential field were obtained to fit twenty-two independently observed experimental data, these being the six vibration frequencies, three Coriolis zeta constants and two centrifugal stretching constants DJ and DJK, for both CH3F and CD3F. The calculations have been repeated both with and without anharmonicity corrections to the vibration frequencies. All the experimental data were weighted according to the reliability of the observations, and the corresponding standard errors and correlation coefficients of the force constants have been deduced. The final force constants are discussed briefly, and compared with previous treatments, particularly with a recent Urey-Bradley treatment for this molecule.

The anharmonic force field of HCN and HCP

The quadratic, cubic, and quartic force field of HCN has been calculated by a least squares refinement to fit the most recent observed data on the vibration-rotation constants of HCN, DCN and H13CN. All of the observed parameters are fitted within their standard errors of observation. The corresponding parameters for other isotopic species are calculated. For HCP and DCP the more limited data available have been fitted to an anharmonic force field using constraints based on comparison with HCN. Using this force field the zero-point rotational constants B0 have been corrected to obtain the equilibrium constants Be, and hence the equilibrium structure has been determined to be re(CH) = 1•0692(7)A, and re(CP) = 1•5398(2)A.