Heterosite effects in novel heteronuclear clusters [OS2Ru(CO)(11)(PPh3)] and Os2Ru(CO)(10)(2-acetylpyridine-N-isopropylimine)]

A new synthetic route towards the mixed-metal cluster [OS2Ru(CO)(12)] is described together with the syntheses of its PPh3 and iPr-AcPy (iPr-AcPy = 2-acetylpyridine-N-isopropylimine) derivatives. The molecular structures of the novel clusters [Os2Ru(CO)(11)(PPh3)] and [Os2Ru(CO)(10)(iPr-AcPy)] were determined on the basis of crystalline solid solutions of the Os2Ru and corresponding Os-3 species. The structures reveal that coordination of the Lewis bases occurs exclusively at the ruthenium site of [Os2Ru(CO)(12)], which is in agreement with density functional theory (DFT) calculations on several structural isomers of these compounds. According to the time-dependent DFT results, the lowest optically accessible excited state of [Os2Ru(CO)(10)(iPr-AcPy)] has a prevailing sigma(Ru-Os-2)pi*(iPr-AcPy) character, with a partial sigma sigma*(Ru-Os-2) contribution. In weakly coordinating 2-chlorobutane, the excited state has a lifetime tau = 10.4 +/- 1.2 ps and produces biradicals considerably faster than observed for [Os-3(CO)10(iPr-AcPy) (tau = 25.3 +/- 0.7ps)]. In coordinating acetonitrile, the excited state of [Os2Ru(CO)(10)(iPr-AcPy)] decays mono-exponentially with a lifetime tau = 2.1 +/- 0.2 ps. In contrast to [Os-3(CO)(10)(iPr-AcPy)] that forms biradicals as the main primary photoproduct even in strongly coordinating solvents, zwitterion formation from the solvated lowest excited state is observed for the heterometallic cluster. This is concluded from time-resolved absorption studies in the microsecond time domain. Due to the lower tendency of the coordinatively unsaturated Ru+(CO)(2)(iPr-AcPy-/0) moiety to bind a Lewis base, the heteronuclear biradical and zwitterionic photoproducts live significantly shorter than their triosmium counterparts. The influence of the weaker Os-2-Ru(iPr-AcPy) bond on the redox reactivity is clearly reflected in very reactive radical anions formed upon electrochemical reduction of [Os2Ru(CO)(10)(iPr-AcPy)]. The dimer [-OS(CO)(4)-Os(CO)(4)-Ru(CO)(2)(iPr-AcPy)](2)(2-) is the only IR-detectable intermediate reduction product. The dinuclear complex [Os-2(CO)(8)](2-) and insoluble [Ru(CO)(2)(iPr-AcPy)](n), are the ultimate reduction products, proving fragmentation of the OS2Ru core.

Distributed water ingress and water potential measurements using fibre optics

We report on a distributed moisture detection scheme which uses a cable design based on waterswellable hydrogel polymers. The cable modulates the loss characteristic of light guided within a multi-mode optical fibre in response to relative water potentials in the surrounding environment. Interrogation of the cable using conventional optical time-domain reflectometry (OTDR) instruments allows water ingress points to be identified and located with a spatial resolution of 50 cm. The system has been tested in a simulated tendon duct grouting experiment as a means of mapping the extent of fill along the duct during the grouting process. Voided regions were detected and identified to within 50 cm. A series of salt solutions has been used to determine the sensor behaviour over a range of water potentials. These experiments predict that measurements of soil moisture content can be made over the range 0 to – 1500 kPa. Preliminary data on soil measurements have shown that the sensor can detect water pressure changes with a resolution of 45 kPa. Applications for the sensor include quality assurance of grouting procedures, verification of waterproofing barriers and soil moisture content determination (for load-bearing calculations).

Multiband OFDM modulation and demodulation for ultra wideband communications

This chapter considers the Multiband Orthogonal Frequency Division Multiplexing (MB- OFDM) modulation and demodulation with the intention to optimize the Ultra-Wideband (UWB) system performance. OFDM is a type of multicarrier modulation and becomes the most important aspect for the MB-OFDM system performance. It is also a low cost digital signal component efficiently using Fast Fourier Transform (FFT) algorithm to implement the multicarrier orthogonality. Within the MB-OFDM approach, the OFDM modulation is employed in each 528 MHz wide band to transmit the data across the different bands while also using the frequency hopping technique across different bands. Each parallel bit stream can be mapped onto one of the OFDM subcarriers. Quadrature Phase Shift Keying (QPSK) and Dual Carrier Modulation (DCM) are currently used as the modulation schemes for MB-OFDM in the ECMA-368 defined UWB radio platform. A dual QPSK soft-demapper is suitable for ECMA-368 that exploits the inherent Time-Domain Spreading (TDS) and guard symbol subcarrier diversity to improve the receiver performance, yet merges decoding operations together to minimize hardware and power requirements. There are several methods to demap the DCM, which are soft bit demapping, Maximum Likelihood (ML) soft bit demapping, and Log Likelihood Ratio (LLR) demapping. The Channel State Information (CSI) aided scheme coupled with the band hopping information is used as a further technique to improve the DCM demapping performance. ECMA-368 offers up to 480 Mb/s instantaneous bit rate to the Medium Access Control (MAC) layer, but depending on radio channel conditions dropped packets unfortunately result in a lower throughput. An alternative high data rate modulation scheme termed Dual Circular 32-QAM that fits within the configuration of the current standard increasing system throughput thus maintaining the high rate throughput even with a moderate level of dropped packets.

Multimodel estimate of the global terrestrial water balance: setup and first results

Six land surface models and five global hydrological models participate in a model intercomparison project (WaterMIP), which for the first time compares simulation results of these different classes of models in a consistent way. In this paper the simulation setup is described and aspects of the multi-model global terrestrial water balance are presented. All models were run at 0.5 degree spatial resolution for the global land areas for a 15-year period (1985-1999) using a newly-developed global meteorological dataset. Simulated global terrestrial evapotranspiration, excluding Greenland and Antarctica, ranges from 415 to 586 mm year-1 (60,000 to 85,000 km3 year-1) and simulated runoff ranges from 290 to 457 mm year-1 (42,000 to 66,000 km3 year-1). Both the mean and median runoff fractions for the land surface models are lower than those of the global hydrological models, although the range is wider. Significant simulation differences between land surface and global hydrological models are found to be caused by the snow scheme employed. The physically-based energy balance approach used by land surface models generally results in lower snow water equivalent values than the conceptual degree-day approach used by global hydrological models. Some differences in simulated runoff and evapotranspiration are explained by model parameterizations, although the processes included and parameterizations used are not distinct to either land surface models or global hydrological models. The results show that differences between model are major sources of uncertainty. Climate change impact studies thus need to use not only multiple climate models, but also some other measure of uncertainty, (e.g. multiple impact models).

Well-posed two-point initial-boundary value problems with arbitrary boundary conditions

We study initial-boundary value problems for linear evolution equations of arbitrary spatial order, subject to arbitrary linear boundary conditions and posed on a rectangular 1-space, 1-time domain. We give a new characterisation of the boundary conditions that specify well-posed problems using Fokas' transform method. We also give a sufficient condition guaranteeing that the solution can be represented using a series. The relevant condition, the analyticity at infinity of certain meromorphic functions within particular sectors, is significantly more concrete and easier to test than the previous criterion, based on the existence of admissible functions.

The impact of resolution on the adjustment and decadal variability of the Atlantic Meridional Overturning Circulation in a coupled climate model

Variations in the Atlantic Meridional Overturning Circulation (MOC) exert an important influence on climate, particularly on decadal time scales. Simulation of the MOC in coupled climate models is compromised, to a degree that is unknown, by their lack of fidelity in resolving some of the key processes involved. There is an overarching need to increase the resolution and fidelity of climate models, but also to assess how increases in resolution influence the simulation of key phenomena such as the MOC. In this study we investigate the impact of significantly increasing the (ocean and atmosphere) resolution of a coupled climate model on the simulation of MOC variability by comparing high and low resolution versions of the same model. In both versions, decadal variability of the MOC is closely linked to density anomalies that propagate from the Labrador Sea southward along the deep western boundary. We demonstrate that the MOC adjustment proceeds more rapidly in the higher resolution model due the increased speed of western boundary waves. However, the response of the Atlantic Sea Surface Temperatures (SSTs) to MOC variations is relatively robust - in pattern if not in magnitude - across the two resolutions. The MOC also excites a coupled ocean-atmosphere response in the tropical Atlantic in both model versions. In the higher resolution model, but not the lower resolution model, there is evidence of a significant response in the extratropical atmosphere over the North Atlantic 6 years after a maximum in the MOC. In both models there is evidence of a weak negative feedback on deep density anomalies in the Labrador Sea, and hence on the MOC (with a time scale of approximately ten years). Our results highlight the need for further work to understand the decadal variability of the MOC and its simulation in climate models.

A model of UK domestic appliance-use using Artificial Neural Networks

The development of an Artificial Neural Network model of UK domestic appliance energy consumption is presented. The model uses diary-style appliance use data and a survey questionnaire collected from 51 households during the summer of 2010. It also incorporates measured energy data and is sensitive to socioeconomic, physical dwelling and temperature variables. A prototype model is constructed in MATLAB using a two layer feed forward network with backpropagation training and has a12:10:24architecture.Model outputs include appliance load profiles which can be applied to the fields of energy planning (micro renewables and smart grids), building simulation tools and energy policy.

Decision making for HVAC&R system selection for a typical office building in the UK

Demands for thermal comfort, better indoor air quality together with lower environmental impacts have had ascending trends in the last decade. In many circumstances, these demands could not be fully covered through the soft approach of bioclimatic design like optimisation of the building orientation and internal layout. This is mostly because of the dense urban environment and building internal energy loads. In such cases, heating, ventilation, air-conditioning and refrigeration (HVAC&R) systems make a key role to fulfill the requirements of indoor environment. Therefore, it is required to select the most proper HVAC&R system. In this study, a robust decision making approach for HVAC&R system selection is proposed. Technical performance, economic aspect and environmental impacts of 36 permutations of primary and secondary systems are taken into account to choose the most proper HVAC&R system for a case study office building. The building is a representative for the dominant form of office buildings in the UK. Dynamic performance evaluation of HVAC&R alternatives using TRNSYS package together with life cycle energy cost analysis provides a reliable basis for decision making. Six scenarios broadly cover the decision makers' attitudes on HVAC&R system selection which are analysed through Analytical Hierarchy Process (AHP). One of the significant outcomes reveals that, despite both the higher energy demand and more investment requirements associated with compound heating, cooling and power system (CCHP); this system is one of the top ranked alternatives due to the lower energy cost and C02 emissions. The sensitivity analysis reveals that in all six scenarios, the first five top ranked alternatives are not changed. Finally, the proposed approach and the results could be used by researchers and designers especially in the early stages of a design process in which all involved bodies face the lack of time, information and tools for evaluation of a variety of systems.

A combined engineering and statistical model of UK domestic appliance electrical load profiles

The development of a combined engineering and statistical Artificial Neural Network model of UK domestic appliance load profiles is presented. The model uses diary-style appliance use data and a survey questionnaire collected from 51 suburban households and 46 rural households during the summer of 2010 and2011 respectively. It also incorporates measured energy data and is sensitive to socioeconomic, physical dwelling and temperature variables. A prototype model is constructed in MATLAB using a two layer feed forward network with back propagation training which has a 12:10:24 architecture. Model outputs include appliance load profiles which can be applied to the fields of energy planning (microrenewables and smart grids), building simulation tools and energy policy.

Reduction of vestigial sideband effects due to multipath transmission in terrestrial broadcast television

In terrestrial television transmission multiple paths of various lengths can occur between the transmitter and the receiver. Such paths occur because of reflections from objects outside the direct transmission path. The multipath signals arriving at the receiver are all detected along with the intended signal causing time displaced replicas called 'ghosts' to appear on the television picture. With an increasing number of people living within built up areas, ghosting is becoming commonplace and therefore deghosting is becoming increasingly important. This thesis uses a deterministic time domain approach to deghosting, resulting in a simple solution to the problem of removing ghosts. A new video detector is presented which reduces the synchronous detector local oscillator phase error, caused by any practical size of ghost, to a lower level than has ever previously been achieved. From the new detector, dispersion of the video signal is minimised and a known closed-form time domain description of the individual ghost components within the detected video is subsequently obtained. Developed from mathematical descriptions of the detected video, a new specific deghoster filter structure is presented which is capable of removing both inphase (I) and also the phase quadrature (Q) induced ghost signals derived from the VSB operation. The new deghoster filter requires much less hardware than any previous deghoster which is capable of removing both I and Q ghost components. A new channel identification algorithm was also required and written which is based upon simple correlation techniques to find the delay and complex amplitude characteristics of individual ghosts. The result of the channel identification is then passed to the new I and Q deghoster filter for ghost cancellation. Generated from the research work performed for this thesis, five papers have been published. D

A robust controller design method for feedback substitution schemes using genetic algorithms

Controllers for feedback substitution schemes demonstrate a trade-off between noise power gain and normalized response time. Using as an example the design of a controller for a radiometric transduction process subjected to arbitrary noise power gain and robustness constraints, a Pareto-front of optimal controller solutions fulfilling a range of time-domain design objectives can be derived. In this work, we consider designs using a loop shaping design procedure (LSDP). The approach uses linear matrix inequalities to specify a range of objectives and a genetic algorithm (GA) to perform a multi-objective optimization for the controller weights (MOGA). A clonal selection algorithm is used to further provide a directed search of the GA towards the Pareto front. We demonstrate that with the proposed methodology, it is possible to design higher order controllers with superior performance in terms of response time, noise power gain and robustness.

Design and management of sustainable built environments

The United Nation Intergovernmental Panel on Climate Change (IPCC) makes it clear that climate change is due to human activities and it recognises buildings as a distinct sector among the seven analysed in its 2007 Fourth Assessment Report. Global concerns have escalated regarding carbon emissions and sustainability in the built environment. The built environment is a human-made setting to accommodate human activities, including building and transport, which covers an interdisciplinary field addressing design, construction, operation and management. Specifically, Sustainable Buildings are expected to achieve high performance throughout the life-cycle of siting, design, construction, operation, maintenance and demolition, in the following areas: • energy and resource efficiency; • cost effectiveness; • minimisation of emissions that negatively impact global warming, indoor air quality and acid rain; • minimisation of waste discharges; and • maximisation of fulfilling the requirements of occupants’ health and wellbeing. Professionals in the built environment sector, for example, urban planners, architects, building scientists, engineers, facilities managers, performance assessors and policy makers, will play a significant role in delivering a sustainable built environment. Delivering a sustainable built environment needs an integrated approach and so it is essential for built environment professionals to have interdisciplinary knowledge in building design and management . Building and urban designers need to have a good understanding of the planning, design and management of the buildings in terms of low carbon and energy efficiency. There are a limited number of traditional engineers who know how to design environmental systems (services engineer) in great detail. Yet there is a very large market for technologists with multi-disciplinary skills who are able to identify the need for, envision and manage the deployment of a wide range of sustainable technologies, both passive (architectural) and active (engineering system),, and select the appropriate approach. Employers seek applicants with skills in analysis, decision-making/assessment, computer simulation and project implementation. An integrated approach is expected in practice, which encourages built environment professionals to think ‘out of the box’ and learn to analyse real problems using the most relevant approach, irrespective of discipline. The Design and Management of Sustainable Built Environment book aims to produce readers able to apply fundamental scientific research to solve real-world problems in the general area of sustainability in the built environment. The book contains twenty chapters covering climate change and sustainability, urban design and assessment (planning, travel systems, urban environment), urban management (drainage and waste), buildings (indoor environment, architectural design and renewable energy), simulation techniques (energy and airflow), management (end-user behaviour, facilities and information), assessment (materials and tools), procurement, and cases studies ( BRE Science Park). Chapters one and two present general global issues of climate change and sustainability in the built environment. Chapter one illustrates that applying the concepts of sustainability to the urban environment (buildings, infrastructure, transport) raises some key issues for tackling climate change, resource depletion and energy supply. Buildings, and the way we operate them, play a vital role in tackling global greenhouse gas emissions. Holistic thinking and an integrated approach in delivering a sustainable built environment is highlighted. Chapter two demonstrates the important role that buildings (their services and appliances) and building energy policies play in this area. Substantial investment is required to implement such policies, much of which will earn a good return. Chapters three and four discuss urban planning and transport. Chapter three stresses the importance of using modelling techniques at the early stage for strategic master-planning of a new development and a retrofit programme. A general framework for sustainable urban-scale master planning is introduced. This chapter also addressed the needs for the development of a more holistic and pragmatic view of how the built environment performs, , in order to produce tools to help design for a higher level of sustainability and, in particular, how people plan, design and use it. Chapter four discusses microcirculation, which is an emerging and challenging area which relates to changing travel behaviour in the quest for urban sustainability. The chapter outlines the main drivers for travel behaviour and choices, the workings of the transport system and its interaction with urban land use. It also covers the new approach to managing urban traffic to maximise economic, social and environmental benefits. Chapters five and six present topics related to urban microclimates including thermal and acoustic issues. Chapter five discusses urban microclimates and urban heat island, as well as the interrelationship of urban design (urban forms and textures) with energy consumption and urban thermal comfort. It introduces models that can be used to analyse microclimates for a careful and considered approach for planning sustainable cities. Chapter six discusses urban acoustics, focusing on urban noise evaluation and mitigation. Various prediction and simulation methods for sound propagation in micro-scale urban areas, as well as techniques for large scale urban noise-mapping, are presented. Chapters seven and eight discuss urban drainage and waste management. The growing demand for housing and commercial developments in the 21st century, as well as the environmental pressure caused by climate change, has increased the focus on sustainable urban drainage systems (SUDS). Chapter seven discusses the SUDS concept which is an integrated approach to surface water management. It takes into consideration quality, quantity and amenity aspects to provide a more pleasant habitat for people as well as increasing the biodiversity value of the local environment. Chapter eight discusses the main issues in urban waste management. It points out that population increases, land use pressures, technical and socio-economic influences have become inextricably interwoven and how ensuring a safe means of dealing with humanity’s waste becomes more challenging. Sustainable building design needs to consider healthy indoor environments, minimising energy for heating, cooling and lighting, and maximising the utilisation of renewable energy. Chapter nine considers how people respond to the physical environment and how that is used in the design of indoor environments. It considers environmental components such as thermal, acoustic, visual, air quality and vibration and their interaction and integration. Chapter ten introduces the concept of passive building design and its relevant strategies, including passive solar heating, shading, natural ventilation, daylighting and thermal mass, in order to minimise heating and cooling load as well as energy consumption for artificial lighting. Chapter eleven discusses the growing importance of integrating Renewable Energy Technologies (RETs) into buildings, the range of technologies currently available and what to consider during technology selection processes in order to minimise carbon emissions from burning fossil fuels. The chapter draws to a close by highlighting the issues concerning system design and the need for careful integration and management of RETs once installed; and for home owners and operators to understand the characteristics of the technology in their building. Computer simulation tools play a significant role in sustainable building design because, as the modern built environment design (building and systems) becomes more complex, it requires tools to assist in the design process. Chapter twelve gives an overview of the primary benefits and users of simulation programs, the role of simulation in the construction process and examines the validity and interpretation of simulation results. Chapter thirteen particularly focuses on the Computational Fluid Dynamics (CFD) simulation method used for optimisation and performance assessment of technologies and solutions for sustainable building design and its application through a series of cases studies. People and building performance are intimately linked. A better understanding of occupants’ interaction with the indoor environment is essential to building energy and facilities management. Chapter fourteen focuses on the issue of occupant behaviour; principally, its impact, and the influence of building performance on them. Chapter fifteen explores the discipline of facilities management and the contribution that this emerging profession makes to securing sustainable building performance. The chapter highlights a much greater diversity of opportunities in sustainable building design that extends well into the operational life. Chapter sixteen reviews the concepts of modelling information flows and the use of Building Information Modelling (BIM), describing these techniques and how these aspects of information management can help drive sustainability. An explanation is offered concerning why information management is the key to ‘life-cycle’ thinking in sustainable building and construction. Measurement of building performance and sustainability is a key issue in delivering a sustainable built environment. Chapter seventeen identifies the means by which construction materials can be evaluated with respect to their sustainability. It identifies the key issues that impact the sustainability of construction materials and the methodologies commonly used to assess them. Chapter eighteen focuses on the topics of green building assessment, green building materials, sustainable construction and operation. Commonly-used assessment tools such as BRE Environmental Assessment Method (BREEAM), Leadership in Energy and Environmental Design ( LEED) and others are introduced. Chapter nineteen discusses sustainable procurement which is one of the areas to have naturally emerged from the overall sustainable development agenda. It aims to ensure that current use of resources does not compromise the ability of future generations to meet their own needs. Chapter twenty is a best-practice exemplar - the BRE Innovation Park which features a number of demonstration buildings that have been built to the UK Government’s Code for Sustainable Homes. It showcases the very latest innovative methods of construction, and cutting edge technology for sustainable buildings. In summary, Design and Management of Sustainable Built Environment book is the result of co-operation and dedication of individual chapter authors. We hope readers benefit from gaining a broad interdisciplinary knowledge of design and management in the built environment in the context of sustainability. We believe that the knowledge and insights of our academics and professional colleagues from different institutions and disciplines illuminate a way of delivering sustainable built environment through holistic integrated design and management approaches. Last, but not least, I would like to take this opportunity to thank all the chapter authors for their contribution. I would like to thank David Lim for his assistance in the editorial work and proofreading.

Femtosecond pulse shaping using differential evolutionary algorithm and wavelet operators

Evolutionary meta-algorithms for pulse shaping of broadband femtosecond duration laser pulses are proposed. The genetic algorithm searching the evolutionary landscape for desired pulse shapes consists of a population of waveforms (genes), each made from two concatenated vectors, specifying phases and magnitudes, respectively, over a range of frequencies. Frequency domain operators such as mutation, two-point crossover average crossover, polynomial phase mutation, creep and three-point smoothing as well as a time-domain crossover are combined to produce fitter offsprings at each iteration step. The algorithm applies roulette wheel selection; elitists and linear fitness scaling to the gene population. A differential evolution (DE) operator that provides a source of directed mutation and new wavelet operators are proposed. Using properly tuned parameters for DE, the meta-algorithm is used to solve a waveform matching problem. Tuning allows either a greedy directed search near the best known solution or a robust search across the entire parameter space.

Terahertz deconvolution

The ability to retrieve information from different layers within a stratified sample using terahertz pulsed reflection imaging and spectroscopy has traditionally been resolution limited by the pulse width available. In this paper, a deconvolution algorithm is presented which circumvents this resolution limit, enabling deep sub-wavelength and sub-pulse width depth resolution. The algorithm is explained through theoretical investigation, and demonstrated by reconstructing signals reflected from boundaries in stratified materials that cannot be resolved directly from the unprocessed time-domain reflection signal. Furthermore, the deconvolution technique has been used to recreate sub-surface images from a stratified sample: imaging the reverse side of a piece of paper.

Multivariate analysis of the dielectric response of materials modeled using networks of resistors and capacitors

We discuss the modeling of dielectric responses of electromagnetically excited networks which are composed of a mixture of capacitors and resistors. Such networks can be employed as lumped-parameter circuits to model the response of composite materials containing conductive and insulating grains. The dynamics of the excited network systems are studied using a state space model derived from a randomized incidence matrix. Time and frequency domain responses from synthetic data sets generated from state space models are analyzed for the purpose of estimating the fraction of capacitors in the network. Good results were obtained by using either the time-domain response to a pulse excitation or impedance data at selected frequencies. A chemometric framework based on a Successive Projections Algorithm (SPA) enables the construction of multiple linear regression (MLR) models which can efficiently determine the ratio of conductive to insulating components in composite material samples. The proposed method avoids restrictions commonly associated with Archie’s law, the application of percolation theory or Kohlrausch-Williams-Watts models and is applicable to experimental results generated by either time domain transient spectrometers or continuous-wave instruments. Furthermore, it is quite generic and applicable to tomography, acoustics as well as other spectroscopies such as nuclear magnetic resonance, electron paramagnetic resonance and, therefore, should be of general interest across the dielectrics community.