The ordering processes of ferroelectric and multiferroic materials were investigated via neutron total scattering and the reverse Monte Carlo method. The results presented in this thesis are from three materials where ferroelectric behaviour is a result of ordering of molecular groups rather than individual atoms. Two of the materials are metal-organic frameworks, three dimensional cage-like structures with guest ions inside the pores; the third material, is a room temperature ferroelectric. In the high-temperature phase of dimethylammonium manganese formate, the framework distorts around the disordered cation, and the cations form shorter hydrogen bonds with the formate framework than the average structure suggests. Framework deformations became increasingly unfavourable as the material cooled. The cations continue to order as the material was cooled below Tc. Analysis of the high-temperature phase atomistic configurations showed that in addition to the three known orientations about the threefold axis, a significant minority of the cations lie mid-way between these positions, a feature which could not have been observed via standard crystallographic techniques. The mechanisms for thermal expansion of potassium imidazolium hexacyanoferrate change between the intermediate-temperature phase and the high-temperature phase. In the hightemperature phase the framework distorts around the disordered guest, but in the intermediatetemperature phase the framework stiffens. I propose that the temperature of the dielectric transition is dependent of the volume inside the framework, but that the temperature range of the intermediate-temperature phase is dependent on the rate of contraction of the framework around the guest cation. For triglycine sulfate no correlation was observed between the orientation of the polar molecules and the motion of the intermediate deuterium. Furthermore, in the high temperature phase the atomistic configurations produced models with macroscopic polarisation. I propose that this material forms domains of aligned polar molecules above Tc and that these domains are larger than the atomistic configurations.

Die Beschaffenheit metallischer Legierungsschmelzen hat einen entscheidenden Einfluss auf die Qualität der festen Legierung. Im Rahmen dieser Diplomarbeit wurde sich gezielt mit der Nahordnung in ternären Ag-Cu-Ge Legierungsschmelzen sowie der binären Randlegierungen beschäftigt. Dazu wurden die Legierungen mithilfe der Röntgendiffraktion untersucht. Zusätzlich wurden die erhaltenen experimentellen Ergebnisse durch Computersimulationen ergänzt und mit Modellrechnungen verglichen.

Silicon (in the form of lithium silicides) has almost ten times the theoretical charge storage capacity of graphite, the anode material used in most commercially-available lithium-ion batteries. Replacing graphite with silicon therefore promises a substantial improvement over the state-of-the-art in electrochemical energy storage. However, it has proved difficult to realise this high theoretical capacity in a practical electrochemical cell and maintain it over repeated charge-discharge cycles. This dissertation presents experimental work probing the changes in local structure occurring during the electrochemical reactions of lithium with silicon, using neutron total scattering and nuclear magnetic resonance, together with novel processing methodologies for analysing the resulting data, in the hope of suggesting ways of improving the performance of silicon-based lithium-ion batteries. Neutron total scattering patterns were obtained from silicon-based anode materials extracted from cells at various states of charge. These samples were composed of a heterogeneous mixture of amorphous, crystalline and disordered crystalline materials. Reverse Monte Carlo is a technique for obtaining structural information from experimental data (particularly total scattering patterns) from amorphous and disordered crystalline materials. However, previously existing Reverse Monte Carlo software could only handle homogeneous materials. Therefore, the RMCprofile software package was extended to handle data from heterogeneous samples. The improved RMCprofile was applied to the aforementioned total scattering patterns, but the much stronger scattering from the other components (themselves not well-characterised) swamped that from the lithium silicide. Future work should attempt to reduce the scattering from the inactive components, particularly the hard-to-model incoherent scattering. NMR data were acquired in situ from silicon-nanowire-based lithium-ion batteries during repeated charge-discharge cycles, achieving much better electrochemical performance than had been seen in previous in situ experiments with silicon. Owing to the large quantities of data obtained, an automated, model-free dimensionality reduction technique was needed. The NMR data were processed using principal component analysis and a variant of non-negative matrix factorisation. With both of these methods, one of the components was found to be associated with high voltages vs. ${Li \vert{} Li^{+}}$ (i.e. a fully discharged anode). This region has seen very little interest by comparison with the low voltage (high levels of lithiation) region of the charge-discharge cycle, so this discovery suggests a new avenue for future research.

Over the years `short-range order' (SRO), whereby the local atomic arrangement differs from that of a random distribution, has been used to explain physical phenomena such as thermodynamic discontinuities, increased strength, anomalous electrical resistivity and magnetic variations in a host of alloys. However, due mainly to experimental difficulties and the complexity of the calculations required for the analysis of diffuse scattering, such work has been largely abandoned and hence quantification and assessment of SRO is notably sparse in the literature. The recent development of reverse Monte-Carlo (RMC) methods for the analysis of total scattering data has opened a promising route for the assessment of a material's local environment and has already provided important insights into a host of complex chemical systems, including liquids, network glasses, nano-materials, functional oxides and metal organic frameworks. The work presented in this thesis focuses on the development of a new methodology for the analysis of local structural effects in metallic systems using total scattering, and the first systematic application to the study of alloys. The simulation of total scattering data from a range of model structures is used to show that the information content of total scattering functions, in particular the pair distribution function (PDF), is sufficiently high to allow the assessment of different types and degrees of short-range order. This is supported by a demonstration of how such orders can be quantified from large box models, produced by fitting total scattering data using the RMC algorithm, with the mathematical analyses outlined. This culminates in a proposed methodology for the analysis of SRO in alloys. Having developed this analytical methodology it is subsequently applied to a number of interesting alloy systems. To demonstrate the efficacy of this methodology it was first applied to the study of a sample of Cu$_{3}$Au - the classically cited case example of a system demonstrating SRO prior to an ordering transition. This experiment provides new insight into this well characterised transition, and also demonstrates the significance of data processing errors on the generation of artefacts in large box modelling. The technique is also applied to the study of the industrially important family of nickel superalloys, assessing ordering in the gamma-phase alloy Ni-Cr and the sublattice orderings occurring in L1$_{2}$ alloys. Next, the use of the technique for the analysis of local strains exhibited in a lattice is presented. A series of models is used to demonstrate how the PDF is expected to change under variations in local strain caused by increased concentration of atomic substitution and variation in atomic radii. This is subsequently used to study the characteristic high-entropy alloy (HEA) CrMnFeCoNi. Through analysis of the PDF, it is demonstrated that the level of local strain exhibited in this alloy is not significantly different from those of other related compositionally simpler alloys. This result is highly significant as it challenges one of the core principles of the field - that the lattices of HEAs are necessarily highly strained. Finally, the energetics of ordering reactions are briefly considered and used to justify some of the observed transformations presented in the earlier work. Together, the body of work in this thesis shows how the total scattering technique can be used to provide valuable insight into a host of interesting local phenomena occurring in alloy systems. It is hoped that this will open up a new field of study into these effects, and ultimately guide the creation of new alloys based on these structure-property relationships.

Bioactive glasses are a class of synthetic inorganic material that have wide orthopedics, dentistry, tissue engineering and other biomedical applications. The origin of the bioactivity is closely related to the atomic structures of these novel glass materials, which otherwise lack long range order and defies any direct experimental measurements due to their amorphous nature. The structure of bioactive glasses is thus essential for the understanding of bioactive behaviors and eventually rational design of glass compositions. In this dissertation, molecular dynamics (MD) and reverse monte carlo (RMC) based computer simulations have been used to systematically study the atomic structure of three classes of new bioactive glasses: strontium doped 45S5 Bioglass®, ZnO-SrO containing bioactive glasses, and Cao-MgO-P2O5-SiO2 bioactive glasses. Properties such as ionic diffusion that are important to glass dissolution behaviors are also examined as a function of glass compositions. The accuracy of structure model generated by simulation was validated by comparing with various experimental measurements including X-ray/neutron diffraction, NMR and Raman spectroscopy. It is shown in this dissertation that atomistic computer simulations, when integrated with structural and property characterizations, is an effective tool in understanding the structural origin of bioactivity and other properties of amorphous bioactive materials that can lead to design of novel materials for biomedical applications.

Die Beschaffenheit metallischer Legierungsschmelzen hat einen entscheidenden Einfluss auf die Qualität der festen Legierung. Im Rahmen dieser Diplomarbeit wurde sich gezielt mit der Nahordnung in ternären Ag-Cu-Ge Legierungsschmelzen sowie der binären Randlegierungen beschäftigt. Dazu wurden die Legierungen mithilfe der Röntgendiffraktion untersucht. Zusätzlich wurden die erhaltenen experimentellen Ergebnisse durch Computersimulationen ergänzt und mit Modellrechnungen verglichen.

An efficient solution method for evaluating radiative transport in a foam layer is a valuable tool for predicting the properties of the layer. Two different solution methods have been investigated. First, a reverse Monte Carlo (RMC) simulation has been developed. In the RMC simulation photon bundles are traced backwards from a detector to the source where they were emitted. The RMC method takes advantage of time reflection symmetry, allowing the photons to be traced backwards in the same manner they are tracked in a standard forward Monte Carlo scheme. Second, a reduced order model based on the singular value decomposition (ROM) has been developed. ROM uses solutions of the reflectance-time profiles found for specific values of the governing parameters to form a solution basis that can be used to generate the profile for any arbitrary values of the parameter set. The governing parameters that were used in this study include the foam layer thickness, the asymmetry parameter, and the scattering coefficient. Layer thicknesses between 4 cm and 20 cm were considered. Values of the asymmetry parameter varied between 0.2 and .08, while the scattering coefficient ranged from 2800 m-1 to 14000 m-1. Ten blind test cases with parameters chosen randomly from these ranges were run and compared to an established forward Monte Carlo (FMC) solution to determine the accuracy and efficiency of both methods. For both RMC and ROM methods the agreement with FMC is good. The average difference in areas under the curves relative to the FMC curve for the ten cases of RMC is 7.1% and for ROM is 7.6%. One of the ten cases causes ROM to extrapolate outside of its data set. If this case is excluded the average error for the remaining nine cases is 5.3%. While the efficiency of RMC for this case is not much greater than that of FMC, it is advantageous in that a solution over a specified time range can be found, as opposed to the FMC where the entire profile must be found. ROM is a very efficient solution method. After a library of solutions is developed, a separated solution with different parameters can be found essentially in real-time. Because of the efficiency of this ROM it is a very promising solution technique for property analysis using inverse methods.

Amorphous transition metal oxides [aTMOs], have emerged as innovative functional materials for wide-ranging electronic, optical and energy-related applications. However, no systematic and broadly applicable method exists to assess their atomic-scale correlations, and since the optical and electronic processes are local structure-dependent, still there are not well-stablished mechanisms that suitably explain the physical properties of aTMOs. This thesis presents experimental and theoretical studies of the atomic short-range order, optical and electronic properties, and state-defects induced by Li+-ion-intercalation and oxygen-vacancies in amorphous titanium aTiO2 and tungsten aWO3 thin-film oxides. Those properties play a key role for application in high energy-density Li+-ion batteries and in switchable dynamical modulation of solar-irradiation transmittance for energy efficient "smart windows", where the disorder-dependent Li+-ion-intercalation and oxygen-vacancy-induced defect-states influence charge-carrier transfer mechanisms. After introducing the scope of this thesis, the fundamental theoretical concepts describing the experimental findings on amorphous solids are reviewed. Thereafter, a comprehensive analysis on the optical absorption phenomena experimentally observed in oxygen-deficient and Li+-ion-intercalated aLixTiO2−y and aLixWO3−y thin-films and a discussion on the electrochromic properties are presented. The optical absorption is described in the framework of the small polaron absorption model. Finally, a state-of-the-art systematic procedure involving theory and experiment in a self-consistent computational framework is implemented to unveil the atomic-scale structure of aTiO2 and aWO3, and its role for the electronic properties. The procedure is based in Reverse Monte Carlo [RMC] and Finite Difference Method [FDM] simulations of X-ray-Absorption spectra to construct a disordered theoretical model having the same bonding and coordination distribution as the experimental system. Ab-initio molecular dynamics simulations and density functional theory are then used to assess defect-states induced by Li+-ion-intercalation and oxygen-vacancies in aTiO2 and aWO3 oxides. The schemes introduced in this study offer a consistent route to experimentally and theoretically assess the role of the atomic-scale structure on the optical and electronic properties of aTiO2 and aWO3 and could be extended to the study of other aTMOs. The final results provide crucial insight towards the understanding of optical and electronic mechanisms where disorder-dependent ion-intercalation and oxygen-vacancy-induced localized defect-states influence charge transfer mechanisms of crucial importance for wide ranging optical and energy-related application of aTiO2 and aWO3 oxides.

Water is an important substance. It is part of us, of our environment, and is a fundamental prerequisite for the existence of life as we know it. The structure of water is still, after over 100 years of research on the subject, however under debate. In this thesis x-ray absorption spectroscopy (XAS) and reverse Monte Carlo (RMC) modeling are used to search for structural solutions of water consistent with many different experimental data sets, with emphasis on the combination of different experimental techniques for a reliable structure determination. Neutron and x-ray diffraction are analyzed in combination with the more recent synchrotron radiation based XAS. Geometrical criteria for H-bonding are implemented in RMC to drive the fits and allow to evaluate differently H-bonded structure models against the data. It is shown that the available diffraction data put little constraints on the type of H-bond topology or O-O-O tetrahedrality for the structure of liquid water. It is also demonstrated that classical MD simulations, using some of the most common interaction potentials for water, give rise to O-O and O-H pair-correlation functions with too sharp first peaks at too short distances to be in agreement with diffraction, and furthermore that requiring a large fraction of broken H-bonds is not in itself enough for a structure model to reproduce the experimental XAS. A contribution to the theoretical description of XAS is made by an in-depth investigation of important technical aspects of the TP-DFT spectrum calculations. A novel approach to RMC, applicable also to data that require a significant amount of computer time to evaluate, is developed which makes use of pre-computed properties from a large set of local geometries allowing RMC simulations directly on data from core-level spectroscopies such as XAS. / At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 4, 5 and 6: Submitted

<p>To estimate the propagation of light in tissue-like optical phantoms (fat emulsions), this thesis utilized the diffuse reflectance spectroscopy in combination with Monte Carlo simulations. A method for determining the two-parametric Gegenbauer-kernal phase function was utilized in order to accurately describe the diffuse reflectance from poly-dispersive scattering optical phantoms with small source-detector separations. The method includes the spectral collimated transmission, spatially resolved diffuse reflectance spectra (SRDR) and the inverse technique of matching spectra from Monte Carlo simulations to those measured. An absolute calibration method using polystyrene micro-spheres was utilized to estimate the relation between simulated and measured SRDR intensities. The phase function parameters were comparable with previous studies and were able to model measured spectra with good accuracy. Significant differences between the phase functions for homogenized milk and the nutritive fat emulsions were found.</p><p> </p>