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Novel disc like molecules based on hexa-n-alkoxy benzoates of triphenylene were synthesised at Hull university. The compounds exhibited thermotropic liquid crystalline behaviour. The compounds differed chemically based upon the number and position of methyl additions to the ester benzoate linkage. Unsymmetrical compounds based on hexa-n-alkoxy triphenylenes were also examined. A number of techniques were employed to observe and measure the physical properties of these compounds. Polarising optical microscopy was used to observe and record the phase behaviour. Typical schlieren nematic textures were often observed in the liquid crystalline phase. The transition temperatures of the phase transitions were recorded to within +/-0.1 °C. Methyl additions to the ester benzoate linkage plays a major role in determining transition temperatures and also the ranges of liquid crystal phase. X-ray diffraction investigations allowed the molecular planar spacings to be measured, use of a heating stage enabled measurements to be taken in the liquid crystalline phase. All the samples produced a diffuse broad diffraction ring in the liquid crystalline phase, indicating that the samples are not highly ordered and that they are likely to have adopted a hexagonal packing arrangement. Planar spacings measured were in the range 22 - 30A, only one sample, DB26, showed a diffraction ring corresponding to a planar spacing of 4.1A, indicating that molecular columns or partial columns were able to form from molecules stacking one on top of another. Thus methyl groups on the ester benzoate linkage disrupt the formation of columns, in turn reducing transition temperatures. A number of methods of successfully aligning the discotic materials using surface treatments are presented. Rubbed PVA and HTAB layers aligned the samples hometropically, while SiO deposited layers aligned the samples homogeneously. (The SiO deposition used an evaporation angle of 45°, a deposition angle of 5° is commonly used to obtain homotropic alignment of calamitic materials.) Methods that produced homogeonous alignment of calamitic materials produced hometropically aligned discotic materials and vice-versa. FTIR allows conformational information about a molecule to be determined. The CH[2] wagging region was investigated to determine conformational information relating to the alkyl arms. Combination of FTIR and aligned samples allowed the alignment process to be investigated, it was determined that the alignment of the molecules occurs in a series of stages, the triphenylene cores align first on cooling, followed by the ester benzoate linkages and finally the alkyl arms. Computer modelling simulations allowed various molecular conformations to be observed, combination with X-ray diffraction data allowed molecular structures to be generated. The software allowed various molecular dimensions to be easily measured and the effect and extent of interdigitation of molecular arms to be observed. The molecular dynamics calculations were only able to calculate energy minimisations for crystalline structures, but the crystalline results offered valuable insights into the liquid crystalline structures and behaviour.

In 1915, Debye derived his well-known equation for the X-ray scattering from a sample of randomly orientated gas-phase molecules. He approximated the molecular scattering by adding the contributions of isolated atomic constituents. This is known as the Independent Atom Model (IAM). However, it omits the redistribution of valence electrons due to bonding, and is limited to the electronic ground state. The main proposition of this thesis is that it is worthwhile going beyond the IAM when interpreting X-ray scattering data. In part, this is motivated by the arrival of new X-ray sources called X-ray Free-Electron Lasers (XFELs). A new method called Ab Initio X-ray Diffraction (AIXRD) is introduced. It calculates the elastic X-ray molecular scattering factor directly from wave functions calculated by ab initio electronic structure theory, for instance Hartree-Fock or multiconfigurational self-consistent field. In this way, the valence electrons are correctly taken into account, and calculations based on electronically excited wave functions become possible. The wave functions must be constructed from spatial orbitals made up of Gaussian-Type Orbitals (GTOs), giving an analytical solution to the Fourier transform integrals involved, and is key to computationally efficient and accurate results. This is compared to a fast Fourier transform (FFT) method, where the electron density is computed on a 3D grid and an FFT algorithm is used to obtain the elastic X-ray molecular scattering factor. Inspired by post-crystallography experiments such as serial femtosecond crystallography and single-particle imaging at XFELs, the AIXRD method is expanded to allow accurate X-ray diffraction calculations from large molecules such as proteins. To make the underlying ab initio problem tractable, the molecule is split into fragments. In other words, the electron density is constructed by a sum of fragment contributions, as is the corresponding molecular form-factor. In this way, it is analogous to the IAM approach except that instead of isolated atoms, there are isolated fragments. A pairwise summation of fragment contributions is also used to account for fragment-fragment interactions. Various fragment definitions are compared based on their effect on the X-ray diffraction signal, and are compared to the IAM method. Finally, X-ray diffraction from molecules in specific quantum states is calculated, revealing a distinct quantum fingerprint in the X-ray diffraction, and a comparison to experiment is made. In particular, the elastic X-ray diffraction is calculated from gas-phase H2 pumped to various electronic, vibrational, and electronic states. This is expanded upon for polyatomic molecules using the harmonic approximation for the vibrational states.

Neutron diffraction is an extremely powerful technique in condensed matter research; it can be used to measure crystallographic structures, including some of those undeterminable using X-rays. It is also perhaps the most powerful technique for determining magnetic structures, and for probing the strength of magnetic interactions, revealing information beyond that extractable from a magnetometer. High pressure is used by many condensed matter researchers as an additional thermodynamic variable, or tool to perturb otherwise stable systems, and has been used with neutron diffraction for many years. When coupled with low temperatures, this has led to the discovery of an enormous range of non-ambient phases of matter, with a range of exotic properties, some of which are discussed in this thesis. Pressure has a very strong effect on the magnetic properties of a material, with many of the most unusual magnetic phases existing only at extremely low temperatures, or pressures which can only be reached on very small samples. The main topic for this thesis is the study, development, and implementation of new techniques to combine low temperatures, high pressures, and neutron diffraction measurements from micro sized samples. A new pressure cell has been designed, tested, and commissioned with neutron beam time on the WISH diffractometer at the ISIS neutron facility. The cell is compact, with a total mass of approximately 5 kg, and is capable of generating large loads in excess of 4.5 tonnes force. Depending on the sample size used with the cell, the opposed anvil system is capable of generating a range of different pressures beyond what is widely available for low temperature neutron diffraction measurements. To save wasted experimental time in cooling and warming the device, the cell is capable of varying the applied load continuously down to 5 K, whilst the sample pressure can also be measured in-situ using a compact spectrometer system. Obtaining refineable neutron diffraction data from the small samples (< 1mm3) possible in an opposed anvil pressure cell is challenging due to extremely low ratios of signal-to-background when compared with large volume pressure cells. Finite element analysis (FEA) was performed to minimise the mass of the cell, whilst also minimising the amount of supporting material in the beam. Despite this, the signal from the sample is typically very weak; to overcome this, a novel 3D printed device has been designed and tested to collimate extremely small samples, removing much of the background signal from the surrounding material. It has enabled neutron data to be collected from samples an order of magnitude smaller than previously measurable in the cell. To maximise the pressures achievable in the pressure cell, for a given sample volume, an extended FEA study was performed to understand the evolutions of stresses in the cell, and understand the limitations of using sapphire as an anvil material. To complement this work, a compact piston cylinder cell has also been designed for a combination of different measurements. One of the key challenges in high pressure research is in knowing, or ensuring, that the conditions the sample is under are approximately the same for a variety of different measurements. Since different instruments, and techniques, may not allow for the same apparatus to be used between them, this is not always possible. A compact clamped piston cylinder cell has been designed, suitable for in-situ electrical measurements, with additional potential for simultaneous neutron diffraction measurements. The device is demonstrated through an ultrasonic characterisation of the compound UGe2. In addition to the information obtainable from neutron diffraction, much can be learnt from studying the transport properties of a material. This information can be used alongside neutron data to provide a full understanding of how a material behaves. One technique of interest measures how the electrical properties of a material changes under applied magnetic field. This is difficult to achieve under pressure due to the often anisotropic construction of the pressure cell affecting the magnetic field on the sample in different orientations, and the challenge in getting wires to the sample under pressure. This thesis presents the design, and preliminary testing, of an ultra compact high symmetry piston cylinder cell designed to be taken to sub-Kelvin temperatures and rotationally oriented in applied magnetic field. The spherical construction of the cell means that the field on the sample position is, to a very close approximation, identical in all orientations. Finally, this thesis presents a study of the binary alloy Pd3Fe under pressure. Pd3Fe was recently reported to undergo a large-volume collapse under high pressure at room temperature, resulting in near zero thermal expansion]. There are several competing theories on the mechanism behind this process. To investigate further, a series of single crystal Pd3Fe samples were grown, cut, prepared, and extensively analysed. The results of this study suggest that the cause for the large volume collapse may not be magnetic in nature, as previously expected.

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In this work monolayers of alkyl amides adsorbed on a graphite surface have been successfully identified and investigated using a combination of synchrotron X-ray and neutron diffraction and Differential Scanning Calorimetry (DSC). Exceptionally stable solid layers have been observed at temperatures well above the bulk melting point, at both high multilayer coverages and, very unusually, at sub-monolayer coverages. The molecular structure of the two-dimensional crystals of these alkyl amides has been obtained from diffraction and interpreted in terms of the subtle intermolecular interactions, particularly the contribution of hydrogen bonding in monolayer assembly. Thermodynamic information provides insight on the mixing behaviour in adsorbed amide layers. A systematic study on the variation in monolayer crystal structures with alkyl chain length (between five and sixteen carbon atoms) of saturated alkyl amides using diffraction identifies that all the amide molecules investigated lie flat on the graphite surface. An odd-even variation isobserved in the monolayer crystal structures and this is supported by the melting enthalpies of the amides determined by DSC. The structure of the even members is found to support the qualitative monolayer arrangement proposed by an STM report of one member of the series, but with more quantitative insight here. Significantly, a new monolayer symmetry group for odd members of the homologous series has been identified. Characteristics of the hydrogen bond geometrybetween the molecules in the solid monolayers are reported exploiting the high level of detail available from the diffraction techniques. Secondly, the formation of solid monolayers of unsaturated alkyl amides has been reported and their crystal structures determined. This is believed to be the first report of these monolayer structures. The position and nature of the double bond have an important effect in the stability of the monolayer. Unusually, certain unsaturated amides that have a double bond conjugated with the amide group are found to form considerably more stable layers than their saturated homologues. The abnormally high melting points and enhanced stability of amide monolayers have been attributed to the existence of a network of hydrogen bonds in the layer. Phase diagrams obtained by DSC for binary mixtures of alkyl amides on graphite have been quantitatively analysed using a combination of thermodynamic models (ideal, eutectic and the regular solution models). The determined mixing behaviour is supported by conclusions based on the monolayer crystal structures of the individual components calculated using diffraction. Saturated amide mixtures that have the same plane group symmetry are found to mix non-ideally in the solid layer and phase separate if the symmetry is different, whereas the mixing behaviour of saturated/unsaturated amides considered here was found to depend on the nature of the double bond (cis/trans). Results from an initial investigation into the adsorption of alkyl amides at the polymer/air interface are also presented. This complements the study above and provides an alternative situation where amide monolayers have a central role. A reduction in the coefficient of friction is seen with increasing bulk concentration of the amide and with increasing time indicating migration of the amide to the surface. A powerful combination of surface reflection techniquesincluding neutron and X-ray reflection and ellipsometry have been used to gain uniquelyquantitative insight into this system. Initial estimates of the concentration of amides at the polystyrene surface are presented for the first time.

Previous work by Heal had shown that X-irradiated sodium azide crystals dissolved in water produced small amounts of nitrogen gas, hydroxyl ion and ammonia, thereby indicating that some decomposition had occurred. Heal also observed colours in the material, similar to those of the X-irradiated alkali halides for which a whole series of colour centres responsible have been postulated. It was therefore decided to investigate the colour centres of the alkali azides, partly to extend the colour centre research, and partly to illuminate the X-ray decomposition processes. Crystalline plates of NaN₃, KN₃, RbN₃ and CsN₃ were irradiated at liquid nitrogen and room temperature, using a Machlett AEG-50 tungsten target X-ray tube, operated at 50 KVP. The absorption spectra of the irradiated samples were measured at liquid nitrogen temperature with a Cary model 14 recording spectrophotometer. The low temperature spectra consisted of three bands. The A band, peaking at 612, 568, 578 and 592 mu for NaN₃, KN₃, RbN₃ and CsN₃, respectively, is ascribed to F centres. The anomalous sodium azide band is related to its trigonal crystal structure, differing from the body centred tetragonal of the other azides. The B band, peaking at 361, 374 and 390 mu for KN₃, RbN₃ and CsN₃ respectively, was strong and triple, there being shoulders about 30 mu on each side of the main peak. For NaN₃ it was weak, single and peaked near 330 mu. Tentatively, it is ascribed to the centre. The C band, peaking about 740, 790, 820 and 850 mu for NaN₃, KN₃, RbN₃ and CsN₃ is weak and single. It may be due to F1 centres. The room temperature spectra were strikingly different from each other, except for RbN₃ and CsN₃. For NaN₃ five bands were observed at 342, 560, 630 , 730 and 860 mu; the latter four were weak and may be an electronic vibrational spectrum. The strong 342 mu band is ascribed to the presence of sodium metal in some non-colloidal form; a correlation between the band and the ionisation potential of the metal is noted. In KN₃ three bands at 760 (strong), 590 (strong shoulder) and 340 mu (weak) were obtained. The first two are ascribed to small F centre aggregates of the M,R type though no definite assignations are made. RbN₃ and CsN₃ spectra both consist of a broad peak showing fine structure, the highest peaks occurring at 330 mu and 375 mu respectively. It is considered uncertain that all the absorption is due to the impurity held responsible for the fine structure. / Science, Faculty of / Chemistry, Department of / Graduate

The structures of four compounds representing each of the organic (natural product), inorganic and organometallic classes of compounds have been determined by single-crystal X-ray diffraction, and the methods employed in solution of the structures have been discussed briefly. For all four structures, the intensity data were collected on a single-crystal diffractometer with [formula omitted] radiation and a scintillation counter. The structure of the alkaloid, daphmacrine methiodide (acetone solvate), was determined from heavy-atom Patterson and Fourier syntheses, and refined by block-diagonal least-squares methods to a final R value of 0.089 for 1834 observed reflections. The absolute configuration was determined by the anomalous dispersion method. The molecule consists of two cage-structures which are linked by a chain of two carbon atoms, and the bond lengths and valency angles do not differ from normal values. 2 4-, For both exo-tricyclo [formula omitted] silver nitrate and silver nitrate itself, the silver ion was determined from Patterson syntheses to be lying in a pseudo-special position, so that the resulting electron-density maps exhibited pseudo-symmetry. A trial-and-error method based on detailed study of the shape of the Ag-Ag Patterson peaks was adopted to find the exact location of the silver ions, and from the resulting electron-density maps the true light atom peaks could be discerned from their images. The refinement was carried out by full-matrix least-squares, and the final R for the complex of silver nitrate was 0.105 and for silver nitrate was 0.067. The structure of the complex consists of thick layers perpendicular to the a crystallographic axis, and separated by ½ a. The silver ion is coordinated roughly tetrahedrally to the double bond of the hydrocarbon (in the exo-position, [formula omitted]), and to three nitrate groups [formula omitted]. The layers are held together by van der Waals forces. The silver nitrate structure consists of layers of silver ions parallel to the b crystallographic axis, and separated by ½ b, with the nitrate groups bridging the gap between layers. Previously observed inequalities in the N—O distances have been removed, all three bond lengths in the nitrate ion being 1.26 (l)Ǻ. The anisotropic thermal motion has been described. The N,N-dimethyl(ferrocenylmethyl)ammonium tetrachlorozincate hydrate structure contains seven heavy atoms, and it was not possible to resolve the Patterson peaks because of the overlap. A direct sign-determining procedure was employed to locate the heavy atoms, and the light atoms were located from resulting electron-density maps. The structure was refined to a final R value of 0.068 for 2012 observed reflections. The mean bond distances are Fe-C = 2. 04Ǻ and C-C (cyclopentadienyl rings) = 1.43Ǻ. Groups of four cations, two anions and two water molecules (two formula units), are linked around centres of symmetry by N-H...Cl (3.11Ǻ), N-H...0 (2.76Ǻ) and 0-H...Cl (3.05, 3.17Ǻ) hydrogen bonds. / Science, Faculty of / Chemistry, Department of / Graduate