Prediction of the equilibrium structures and photomagnetic properties of the Prussian blue analogue RbMn[Fe(CN)6] by density functional theory

A periodic density functional theory method using the B3LYP hybrid exchange-correlation potential is applied to the Prussian blue analogue RbMn[Fe(CN)6] to evaluate the suitability of the method for studying, and predicting, the photomagnetic behavior of Prussian blue analogues and related materials. The method allows correct description of the equilibrium structures of the different electronic configurations with regard to the cell parameters and bond distances. In agreement with the experimental data, the calculations have shown that the low-temperature phase (LT; Fe(2+)(t(6)2g, S = 0)-CN-Mn(3+)(t(3)2g e(1)g, S = 2)) is the stable phase at low temperature instead of the high-temperature phase (HT; Fe(3+)(t(5)2g, S = 1/2)-CN-Mn(2+)(t(3)2g e(2)g, S = 5/2)). Additionally, the method gives an estimation for the enthalpy difference (HT LT) with a value of 143 J mol(-1) K(-1). The comparison of our calculations with experimental data from the literature and from our calorimetric and X-ray photoelectron spectroscopy measurements on the Rb0.97Mn[Fe(CN)6]0.98 x 1.03 H2O compound is analyzed, and in general, a satisfactory agreement is obtained. The method also predicts the metastable nature of the electronic configuration of the high-temperature phase, a necessary condition to photoinduce that phase at low temperatures. It gives a photoactivation energy of 2.36 eV, which is in agreement with photoinduced demagnetization produced by a green laser.

The interplay between microscopic and mesoscopic structures in complex networks

Understanding a complex network's structure holds the key to understanding its function. The physics community has contributed a multitude of methods and analyses to this cross-disciplinary endeavor. Structural features exist on both the microscopic level, resulting from differences between single node properties, and the mesoscopic level resulting from properties shared by groups of nodes. Disentangling the determinants of network structure on these different scales has remained a major, and so far unsolved, challenge. Here we show how multiscale generative probabilistic exponential random graph models combined with efficient, distributive message-passing inference techniques can be used to achieve this separation of scales, leading to improved detection accuracy of latent classes as demonstrated on benchmark problems. It sheds new light on the statistical significance of motif-distributions in neural networks and improves the link-prediction accuracy as exemplified for gene-disease associations in the highly consequential Online Mendelian Inheritance in Man database. © 2011 Reichardt et al.

A comparative study of 'joined-up' working in three regeneration programme case studies

This research concerns the development of coordination and co-governance within three different regeneration programmes within one Midlands city over the period from 1999 to 2002. The New Labour government, in office since 1997, had an agenda for ‘joining-up’ government, part of which has had considerable impact in the area of regeneration policy. Joining-up government encompasses a set of related activities which can include the coordination of policy-making and service delivery. In regeneration, it also includes a commitment to operate through co-governance. Central government and local and regional organisations have sought to put this idea into practice by using what may be referred to as network management processes. Many characteristics of new policies are designed to address the management of networks. Network management is not new in this area, it has developed at least since the early 1990s with the City Challenge and Single Regeneration Budget (SRB) programmes as a way of encouraging more inclusive and effective regeneration interventions. Network management theory suggests that better management can improve decision-making outcomes in complex networks. The theories and concepts are utilised in three case studies as a way of understanding how and why regeneration attempts demonstrate real advances in inter-organisational working at certain times whilst faltering at others. Current cases are compared to the historical case of the original SRB programme as a method of assessing change. The findings suggest that: The use of network management can be identified at all levels of governance. As previous literature has highlighted, central government is the most important actor regarding network structuring. However, it can be argued that network structuring and game management are both practised by central and local actors; Furthermore, all three of the theoretical perspectives within network management (Instrumental, Institutional and Interactive), have been identified within UK regeneration networks. All may have a role to play with no single perspective likely to succeed on its own. Therefore, all could make an important contribution to the understanding of how groups can be brought together to work jointly; The findings support Klijn’s (1997) assertion that the institutional perspective is dominant for understanding network management processes; Instrumentalism continues on all sides, as the acquisition of resources remains the major driver for partnership activity; The level of interaction appears to be low despite the intentions for interactive decision-making; Overall, network management remains partial. Little attention is paid to the issues of accountability or to the institutional structures which can prevent networks from implementing the policies designed by central government, and/or the regional tier.

Corporate governance in the NHS

Corporate Governance - which is concerned with the management and direction of organizations at the very highest level - has grown in importance in the private sector, from where the concept largely derives, as a result mainly of malpractice. As a consequence, interest in the topic has grown steadily, largely on the part of Governments, regulators and academics. Managerial reforms of the NHS introduced refashioned District Health Authorities (DHAs) which mimic the role and structure of the Company board. The research reported in this thesis is an assessment of corporate governance in post reform English DHAs. The research examines the characteristics of directors, the extent to which corporate governance can be empirically demonstrated, the extent to which it is consistent with the Working for Patients reforms, and, the consequences of such changes for the development of directors and of DHAs. The research also considers the relevance of the findings to other parts of the NHS and public sector. The work draws upon the conceptual framework established by Tricker (1984; also Hilmer & Tricker 1991) with detailed survey and case study findings concerned with issues of direction, executive management, supervision and accountability. The findings from this new research make an important contribution to the policy debate and to the literature(s) concerned.

Collaborative enterprise governance : sustainable management of inter-firm R&D relationships in the German car industry

This research reports on the appropriate governance, i.e. design and management, of inter-firm R&D relationships in order to achieve sustainable competitive success for the whole partnership as well as its individual members. An exploratory study in the German automotive industry using inductive Grounded Theory was conducted. This involved data collection via 28 semi-structured interviews with 16 companies in order to form a set of 35 tentative propositions that have been validated via a questionnaire survey receiving 110 responses from 52 companies. The research has resulted in the consolidation of the validated propositions into a novel concept termed Collaborative Enterprise Governance. The core of the concept is a competence based contingency framework that helps decision makers in selecting the most appropriate governance strategy (i.e. sourcing strategy) for an inter-firm R&D relationship between a buyer and its supplier. Thereby, the concept does not draw on whole company-to-company connectivity. It rather conceptualises an inter-firm relationship to be composed of autonomous cross-functional units of the individual partner companies that contribute value to a particular joint R&D project via the possession of task specific competencies. The novel concept and its elements have been evaluated in a focus group with industrial experts of the German automotive industry and revealed positive effects on the sustainable competitive success of the whole partnership and the individual partner companies. However, it also showed that current practice does not apply the right mechanisms for its implementation and hence guidelines for practitioners and decision makers involved in inter-firm R&D collaboration in the automotive industry are offered on how to facilitate the implementation and usage of the Collaborative Enterprise Governance philosophy.

Nuclear magnetic resonance studies of molecular interactions and structures

This thesis is concerned with the investigation, by nuclear magnetic resonance spectroscopy, of the molecular interactions occurring in mixtures of benzene and cyclohexane to which either chloroform or deutero-chloroform has been added. The effect of the added polar molecule on the liquid structure has been studied using spin-lattice relaxation time, 1H chemical shift, and nuclear Overhauser effect measurements. The main purpose of the work has been to validate a model for molecular interaction involving local ordering of benzene around chloroform. A chemical method for removing dissolved oxygen from samples has been developed to encompass a number of types of sample, including quantitative mixtures, and its supremacy over conventional deoxygenation technique is shown. A set of spectrometer conditions, the use of which produces the minimal variation in peak height in the steady state, is presented. To separate the general diluting effects of deutero-chloroform from its effects due to the production of local order a series of mixtures involving carbon tetrachloride, instead of deutero-chloroform, have been used as non-interacting references. The effect of molecular interaction is shown to be explainable using a solvation model, whilst an approach involving 1:1 complex formation is shown not to account for the observations. It is calculated that each solvation shell, based on deutero-chloroform, contains about twelve molecules of benzene or cyclohexane. The equations produced to account for the T1 variations have been adapted to account for the 1H chemical shift variations in the same system. The shift measurements are shown to substantiate the solvent cage model with a cage capacity of twelve molecules around each chloroform molecule. Nuclear Overhauser effect data have been analysed quantitatively in a manner consistent with the solvation model. The results show that discrete shells only exist when the mole fraction of deutero-chloroform is below about 0.08.

An investigation into the network structures of eThylene propylene terpolymer elastomers

A series of ethylene propylene terpolymer vulcanizates, prepared by varying termonomer type, cure system, cure time and cure temperature, are characterized by determining the number and type of cross-links present. The termonomers used represent the types currently available in commercial quantities. Characterization is carried out by measuring the C1 constant of the Mooney Rivlin Saunders equation before and after treatment with the chemical probes propane-2-thiol/piperidine and n-hexane thiol/piperidine, thus making it possible to calculate the relative proportions of mono-sulphidic, di-sulphidic and poly- sulphidic cross-links. The cure systems used included both sulphur and peroxide formulations. Specific physical properties are determined for each network and an attempt is made to correlate observed changes in these with variations in network structure. A survey of the economics of each formulation based on a calculated efficiency parameter for each cure system is included. Values of C1 are calculated from compression modulus data after the reliability of the technique when used with ethylene propylene terpolymers had been established. This is carried out by comparing values from both compression and extension stress strain measurements for natural rubber vulcanizates and by assessing the effects of sample dimensions and the degree of swelling. The technique of compression modulus is much more widely applicable than previously thought. The basic structure of an ethylene propylene terpolymer network appears to be independent of the type of cure system used ( sulphur based systems only), the proportions of constituent cross-links being nearly constant.

Damage analysis of bridge structures using vibrational techniques

Much research is currently centred on the detection of damage in structures using vibrational data. The work presented here examined several areas of interest in support of a practical technique for identifying and locating damage within bridge structures using apparent changes in their vibrational response to known excitation. The proposed goals of such a technique included the need for the measurement system to be operated on site by a minimum number of staff and that the procedure should be as non-invasive to the bridge traffic-flow as possible. Initially the research investigated changes in the vibrational bending characteristics of two series of large-scale model bridge-beams in the laboratory and these included ordinary-reinforced and post-tensioned, prestressed designs. Each beam was progressively damaged at predetermined positions and its vibrational response to impact excitation was analysed. For the load-regime utilised the results suggested that the infuced damage manifested itself as a function of the span of a beam rather than a localised area. A power-law relating apparent damage with the applied loading and prestress levels was then proposed, together with a qualitative vibrational measure of structural damage. In parallel with the laboratory experiments a series of tests were undertaken at the sites of a number of highway bridges. The bridges selected had differing types of construction and geometric design including composite-concrete, concrete slab-and-beam, concrete-slab with supporting steel-troughing constructions together with regular-rectangular, skewed and heavily-skewed geometries. Initial investigations were made of the feasibility and reliability of various methods of structure excitation including traffic and impulse methods. It was found that localised impact using a sledge-hammer was ideal for the purposes of this work and that a cartridge `bolt-gun' could be used in some specific cases.

Damage location in structures by monitoring vibration characteristics

The aim of this work was to investigate the feasibility of detecting and locating damage in large frame structures where visual inspection would be difficult or impossible. This method is based on a vibration technique for non-destructively assessing the integrity of structures by using measurements of changes in the natural frequencies. Such measurements can be made at a single point in the structure. The method requires that initially a comprehensive theoretical vibration analysis of the structure is undertaken and from it predictions are made of changes in dynamic characteristics that will occur if each member of the structure is damaged in turn. The natural frequencies of the undamaged structure are measured, and then routinely remeasured at intervals . If a change in the natural frequencies is detected a statistical method. is used to make the best match between the measured changes in frequency and the family of theoretical predictions. This predicts the most likely damage site. The theoretical analysis was based on the finite element method. Many structures were extensively studied and a computer model was used to simulate the effect of the extent and location of the damage on natural frequencies. Only one such analysis is required for each structure to be investigated. The experimental study was conducted on small structures In the laboratory. Frequency changes were found from inertance measurements on various plane and space frames. The computational requirements of the location analysis are small and a desk-top micro computer was used. Results of this work showed that the method was successful in detecting and locating damage in the test structures.

System identification of linear vibrating structures

Methods of dynamic modelling and analysis of structures, for example the finite element method, are well developed. However, it is generally agreed that accurate modelling of complex structures is difficult and for critical applications it is necessary to validate or update the theoretical models using data measured from actual structures. The techniques of identifying the parameters of linear dynamic models using Vibration test data have attracted considerable interest recently. However, no method has received a general acceptance due to a number of difficulties. These difficulties are mainly due to (i) Incomplete number of Vibration modes that can be excited and measured, (ii) Incomplete number of coordinates that can be measured, (iii) Inaccuracy in the experimental data (iv) Inaccuracy in the model structure. This thesis reports on a new approach to update the parameters of a finite element model as well as a lumped parameter model with a diagonal mass matrix. The structure and its theoretical model are equally perturbed by adding mass or stiffness and the incomplete number of eigen-data is measured. The parameters are then identified by an iterative updating of the initial estimates, by sensitivity analysis, using eigenvalues or both eigenvalues and eigenvectors of the structure before and after perturbation. It is shown that with a suitable choice of the perturbing coordinates exact parameters can be identified if the data and the model structure are exact. The theoretical basis of the technique is presented. To cope with measurement errors and possible inaccuracies in the model structure, a well known Bayesian approach is used to minimize the least squares difference between the updated and the initial parameters. The eigen-data of the structure with added mass or stiffness is also determined using the frequency response data of the unmodified structure by a structural modification technique. Thus, mass or stiffness do not have to be added physically. The mass-stiffness addition technique is demonstrated by simulation examples and Laboratory experiments on beams and an H-frame.

The effects of new technology on employment structures in the service sector

This thesis explores the interrelationships between the labour process, the development of technology and patterns of gender differentiation. The introduction of front office terminals into building society branches forms the focus of the research. Case studies were carried out in nine branches, three each from three building societies. Statistical data for the whole movement and a survey of ten of the top thirty societies provided the context for the studies. In the process of the research it became clear that it was not technology itself but the way that it was used, that was the main factor in determining outcomes. The introduction of new technologies is occurring at a rapid pace, facilitated by continuing high growth rates, although front office technology could seldom be cost justified. There was great variety between societies in their operating philosophies and their reasons for and approach to computerisation, but all societies foresaw an ultimate saving in staff. Computerisation has resulted in the deskilling of the cashiering role and increased control over work at all stages. Some branch managers experienced a decrease in autonomy and an increase in control over their work. Subsequent to this deskilling there has been a greatly increased use of part time staff which has enabled costs to be reduced. There has also been a polarisation between career and non-career staff which, like the use of part time staff, has occurred along gender lines. There is considerable evidence that societies' policies, structures and managerial attitudes continue to directly and indirectly discriminate against women. It is these practices which confine women to lower grades and ensure their dependence on the family and which create the pool of cheap skilled labour that societies so willingly exploit by increasing part time work. Gender strategies enter management strategies throughout the operations of the organisation.

The European Union and global governance:a handbook

The role of the European Union in global politics has been of growing interest over the past decade. The EU is a key player in global institutions such as the World Trade Organization (WTO) and NATO. It continues to construct an emerging identity and project its values and interests throughout contemporary international relations. The capacity of the EU to both formulate and realise its goals, however, remains contested. Some scholars claim the EU’s `soft power’ attitude rivals that of the USA’s `hard power’ approach to international relations. Others view the EU as insufficiently able to produce a co-ordinated position to project upon global politics. Regardless of the position taken within this debate, the EU’s relationship with its external partners has an increasingly important impact upon economic, political and security concerns on an international level. Trade negotiations, military interventions, democracy promotion, international development and responses to the global economic crisis have all witnessed the EU playing a central role. This has seen the EU become both a major force in contemporary institutions of global governance and a template for supranational governance that might influence other attempts to construct regional and global institutions. This volume brings together a collection of leading EU scholars to provide a state-of-the-art overview covering these and other debates relating to the EU’s role in contemporary global governance. The Handbook is divided into four main sections: Part I: European studies and global governance – provides an overview and critical assessment of the leading theoretical approaches through which the EU’s role in global governance has been addressed within the literature. Part II: Institutions – examines the role played by the key EU institutions in pursuing a role for the EU in contemporary international relations. Part III: Policy and issue areas – explores developments within particular policy sectors, assessing the different impact that the EU has had in different issue areas, including foreign and security policy, environmental policy, common commercial policy, the Common Agricultural Policy, development policy, accession policy, the Neighbourhood Policy and conflict transformation. Part IV: The global multilevel governance complex and the EU – focuses on the relationship between the EU and the institutions, regions and countries with which it forms a global multilevel governance complex, including chapters on the EU’s relationship with the WTO, United Nations, East Asia, Africa and the USA.

Elastic-plastic analysis of complete building structures

In this Thesis, details of a proposed method for the elastic-plastic failure load analysis of complete building structures are given. In order to handle the problem, a computer programme in Atlas Autocode is produced. The structures consist of a number of parallel shear walls and intermediate frames connected by floor slabs. The results of an experimental investigation are given to verify the theoretical results and to demonstrate various factors that may influence the behaviour of these structures. Large full scale practical structures are also analysed by the proposed method and suggestions are made for achieving design economy as well as for extending research in various aspects of this field. The existing programme for elastic-plastic analysis of large frames is modified to allow for the effect of composite action of structural members, i.e. reinforced concrete floor slabs and the supporting steel beams. This modified programme is used to analyse some framed type structures with composite action as well as those which incorporate plates and shear walls. The results obtained are studied to ascertain the influence of composite action and other factors on the load carrying capacity of both bare frames and complete building structures. The theoretical failure load presented in this thesis does not predict the overall failure load of the structure nor does it predict the partial failure load of the shear walls and slabs but it merely predicts the partial failure load of a single frame and assumes that the loss of stiffess of such a frame renders the overall structure unusable. For most structures the analysis proposed in this thesis is likely to break down prematurely due to the failure of the slab and shear wall system and this factor must be taken into account in any future work on such structures. The experimental work reported in this thesis is acknowledged to be unsatisfactory as a verification of the limited theory proposed. In particular perspex was not found to be a suitable material for testing at high loads, micro-concrete may be more suitable.

Behaviour of concrete frame structures under localised fire scenarios

This thesis encompasses an investigation of the behaviour of concrete frame structure under localised fire scenarios by implementing a constitutive model using finite-element computer program. The investigation phase included properties of material at elevated temperature, description of computer program, thermal and structural analyses. Transient thermal properties of material have been employed in this study to achieve reasonable results. The finite-element computer package of ANSYS is utilized in the present analyses to examine the effect of fire on the concrete frame under five various fire scenarios. In addition, a report of full-scale BRE Cardington concrete building designed to Eurocode2 and BS8110 subjected to realistic compartment fire is also presented. The transient analyses of present model included additional specific heat to the base value of dry concrete at temperature 100°C and 200°C. The combined convective-radiation heat transfer coefficient and transient thermal expansion have also been considered in the analyses. For the analyses with the transient strains included, the constitutive model based on empirical formula in a full thermal strain-stress model proposed by Li and Purkiss (2005) is employed. Comparisons between the models with and without transient strains included are also discussed. Results of present study indicate that the behaviour of complete structure is significantly different from the behaviour of individual isolated members based on current design methods. Although the current tabulated design procedures are conservative when the entire building performance is considered, it should be noted that the beneficial and detrimental effects of thermal expansion in complete structures should be taken into account. Therefore, developing new fire engineering methods from the study of complete structures rather than from individual isolated member behaviour is essential.

The discourse of academic seminars:structures and strategies of interaction

Seminar discussion is an important mode of instruction in Higher Education. However, the discourse of discussion in academic seminars has been little investigated. Until now, there has existed only a limited amount of empirically based language description which could be used to inform those working in the field of English for Academic Purposes. The present study investigates discussion in seminars on a MBA programme and offers frameworks to account for central aspects of the verbal interaction: exchange patterns; acts and moves initiating exchanges and strategies. Three subgenres of seminar discussion are examined: the discussion following the presentation by an outside speaker; the discussion following the presentation by students and non-presentation tutorial discussion. Exchanges are found to be basically two-part structures of initiation and response. Some extended patterns are brought to light and it is argued that the major impetus prolonging exchanges in discussion is a third-part move registering dissatisfaction with the initial responses given. Exchanges are observed to be driven by moves functioning as elicitations although acts at initiation both ask for information and ideas and propose them. Initiation may be complex and involves a mixture of the acts. Textual signalling and attitudinal strategies used in seminars are explicated. The latter are accounted for in terms of the face concerns of the speakers. The features are examined across the three subgenres. Some quantitative variations were observed. These variations are discussed in the light of situational variables such as levels of participant status and knowledge. Theoretical implications are drawn and applications for syllabus and methodology in English for Academic Purposes are suggested.