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).

Generation of inertia-gravity waves in the rotating thermal annulus by a localised boundary layer instability

Waves with periods shorter than the inertial period exist in the atmosphere (as inertia-gravity waves) and in the oceans (as Poincaré and internal gravity waves). Such waves owe their origin to various mechanisms, but of particular interest are those arising either from local secondary instabilities or spontaneous emission due to loss of balance. These phenomena have been studied in the laboratory, both in the mechanically-forced and the thermally-forced rotating annulus. Their generation mechanisms, especially in the latter system, have not yet been fully understood, however. Here we examine short period waves in a numerical model of the rotating thermal annulus, and show how the results are consistent with those from earlier laboratory experiments. We then show how these waves are consistent with being inertia-gravity waves generated by a localised instability within the thermal boundary layer, the location of which is determined by regions of strong shear and downwelling at certain points within a large-scale baroclinic wave flow. The resulting instability launches small-scale inertia-gravity waves into the geostrophic interior of the flow. Their behaviour is captured in fully nonlinear numerical simulations in a finite-difference, 3D Boussinesq Navier-Stokes model. Such a mechanism has many similarities with those responsible for launching small- and meso-scale inertia-gravity waves in the atmosphere from fronts and local convection.

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.

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

Promotion carryover as a missing data problem

An important feature of agribusiness promotion programs is their lagged impact on consumption. Efficient investment in advertising requires reliable estimates of these lagged responses and it is desirable from both applied and theoretical standpoints to have a flexible method for estimating them. This note derives an alternative Bayesian methodology for estimating lagged responses when investments occur intermittently within a time series. The method exploits a latent-variable extension of the natural-conjugate, normal-linear model, Gibbs sampling and data augmentation. It is applied to a monthly time series on Turkish pasta consumption (1993:5-1998:3) and three, nonconsecutive promotion campaigns (1996:3, 1997:3, 1997:10). The results suggest that responses were greatest to the second campaign, which allocated its entire budget to television media; that its impact peaked in the sixth month following expenditure; and that the rate of return (measured in metric tons additional consumption per thousand dollars expended) was around a factor of 20.

A spatio-temporal structure-based approach to drought characterisation

Drought characterisation is an intrinsically spatio-temporal problem. A limitation of previous approaches to characterisation is that they discard much of the spatio-temporal information by reducing events to a lower-order subspace. To address this, an explicit 3-dimensional (longitude, latitude, time) structure-based method is described in which drought events are defined by a spatially and temporarily coherent set of points displaying standardised precipitation below a given threshold. Geometric methods can then be used to measure similarity between individual drought structures. Groupings of these similarities provide an alternative to traditional methods for extracting recurrent space-time signals from geophysical data. The explicit consideration of structure encourages the construction of summary statistics which relate to the event geometry. Example measures considered are the event volume, centroid, and aspect ratio. The utility of a 3-dimensional approach is demonstrated by application to the analysis of European droughts (15 °W to 35°E, and 35 °N to 70°N) for the period 1901–2006. Large-scale structure is found to be abundant with 75 events identified lasting for more than 3 months and spanning at least 0.5 × 106 km2. Near-complete dissimilarity is seen between the individual drought structures, and little or no regularity is found in the time evolution of even the most spatially similar drought events. The spatial distribution of the event centroids and the time evolution of the geographic cross-sectional areas strongly suggest that large area, sustained droughts result from the combination of multiple small area (∼106 km2) short duration (∼3 months) events. The small events are not found to occur independently in space. This leads to the hypothesis that local water feedbacks play an important role in the aggregation process.

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.

Terahertz pulse imaging of stratified architectural materials for cultural heritage studies

Terahertz pulse imaging (TPI) is a novel noncontact, nondestructive technique for the examination of cultural heritage artifacts. It has the advantage of broadband spectral range, time-of-flight depth resolution, and penetration through optically opaque materials. Fiber-coupled, portable, time-domain terahertz systems have enabled this technique to move out of the laboratory and into the field. Much like the rings of a tree, stratified architectural materials give the chronology of their environmental and aesthetic history. This work concentrates on laboratory models of stratified mosaics and fresco paintings, specimens extracted from a neolithic excavation site in Catalhoyuk, Turkey, and specimens measured at the medieval Eglise de Saint Jean-Baptiste in Vif, France. Preparatory spectroscopic studies of various composite materials, including lime, gypsum and clay plasters are presented to enhance the interpretation of results and with the intent to aid future computer simulations of the TPI of stratified architectural material. The breadth of the sample range is a demonstration of the cultural demand and public interest in the life history of buildings. The results are an illustration of the potential role of TPI in providing both a chronological history of buildings and in the visualization of obscured wall paintings and mosaics.

Terahertz pulse investigation of paleolithic wall etchings

Results are presented of an examination of flow rock-covered Paleoloithic cave art using time-domain terahertz reflectometry.

Improvements in Aerosol Optical Depth Estimation Using Multiangle CHRIS/PROBA Images

A method has been developed to estimate aerosol optical depth (AOD) over land surfaces using high spatial resolution, hyperspectral, and multiangle Compact High Resolution Imaging Spectrometer (CHRIS)/Project for On Board Autonomy (PROBA) images. The CHRIS instrument is mounted aboard the PROBA satellite and provides up to 62 bands. The PROBA satellite allows pointing to obtain imagery from five different view angles within a short time interval. The method uses inversion of a coupled surface/atmosphere radiative transfer model and includes a general physical model of angular surface reflectance. An iterative process is used to determine the optimum value providing the best fit of the corrected reflectance values for a number of view angles and wavelengths with those provided by the physical model. This method has previously been demonstrated on data from the Advanced Along-Track Scanning Radiometer and is extended here to the spectral and angular sampling of CHRIS/PROBA. The values obtained from these observations are validated using ground-based sun-photometer measurements. Results from 22 image sets show an rms error of 0.11 in AOD at 550 nm, which is reduced to 0.06 after an automatic screening procedure.

Terahertz pulse imaging in archaeology

The work presented in this article was performed at the Oriental Institute at the University of Chicago, on objects from their permanent collection: an ancient Egyptian bird mummy and three ancient Sumerian corroded copper-alloy objects. We used a portable, fiber-coupled terahertz time-domain spectroscopic imaging system, which allowed us to measure specimens in both transmission and reflection geometry, and present time- and frequency-based image modes. The results confirm earlier evidence that terahertz imaging can provide complementary information to that obtainable from x-ray CT scans of mummies, giving better visualisation of low density regions. In addition, we demonstrate that terahertz imaging can distinguish mineralized layers in metal artifacts.