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Intrinsic Quantum Thermodynamics (IQT) is a theory that combines Thermodynamics and Quantum Mechanics into a single theory and asserts that irreversibility and the increase of entropy has its origin at the fundamental, atomistic level. The merits and details of IQT are discussed and compared with the well-known theory of Quantum Statistical Mechanics (QSM) and the more recent development of Quantum Thermodynamics (QT). IQT is then used to model in 3D the time evolution of the adsorption of hydrogen on a single-walled carbon nanotube. The initial state of the hydrogen molecules is far from stable equilibrium and over time the system relaxes to a state of stable equilibrium with the hydrogen near the walls of the carbon nanotube. The details of the model are presented, which include the construction of the energy eigenlevels for the system, the treatment of the interactions between the hydrogen and the nanotube along with the interactions of the hydrogen molecules with each other, and the solution of the IQT equation of motion as well as approximation methods that are developed to deal with extremely large numbers of energy eigenlevels. In addition, a new extension to the theory of IQT is proposed for modeling systems that undergo heat interactions with a heat reservoir. The formulation of a new heat interaction operator is discussed, implemented, tested, and compared with a previous version extant in the literature. IQT theory is then further extended to encompass simple mass interactions with a mass reservoir. The formulation, implementation, and testing of the mass interaction operator is also discussed in detail. Finally, IQT is used to model the results of two experiments found in the literature. The first experiment deals with the spin relaxation of rubidium atoms and the second tests the relaxation behavior of single trapped ion that is allowed to interact with an external heat reservoir. Good agreement between experiment and the model predictions is found. / Ph. D.

This Thesis considers the use of solid-state metal ammines as ammonia storage materials and endeavours to understand these materials on a fundamental chemical level. The ammines of LiBH₄, MgCl₂, MgBr₂, MgI₂ and Mg(BH₄)₂, are investigated. The structures of lithium borohydride ammines, Li(NH₃)_nBH₄ with n = 1, 2, 3 and 4 are solved using X-ray and neutron diffraction, vibrational spectroscopy, nuclear magnetic resonance, and first-principles calculations. The reversibility, bonding and ammonia storage properties of this system are discussed, and investigated using gravimetric analysis and vibrational spectroscopy. The ammines of magnesium halides are investigated using X-ray and neutron powder diffraction, gravimetric techniques, nuclear magnetic resonance, first-principles calculations and vibrational spectroscopy. Their disordered structures, bonding, and decomposition are discussed, and the trends in their properties are used to interpret the properties of other ammines. The ammines of magnesium borohydride are investigated using X-ray and neutron powder diffraction, gravimetric techniques, first-principles calculations and vibrational spectroscopy. The structure, decomposition and reversibility of Mg(NH₃)₆(BH₄)₂ as an ammonia store are presented. Throughout the Thesis and at the end of each Chapter the possibility of using these ammines as solid-state ammonia stores is discussed.

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This thesis reports the investigation of molecular materials for hydrogen storage applications with a particular emphasis on alkali-metal amidoboranes. I have developed new routes for the synthesis of $alpha$-LiNH$_{2}$BH$_{3}$ and NaNH$_{2}$BH$_{3}$, and have studied their hydrogen storage properties by thermogravimetric analysis, variable temperature X-ray and neutron diffraction and inelastic neutron scattering. I report the synthesis and full structural characterization of two new materials, KNH$_{2}$BH$_{3}$ and $beta$-LiNH$_{2}$BH$_{3}$, and have performed initial studies on a tetragonal phase of a variant of LiNH$_{2}$BH$_{3}$ with a preliminary structure solution. I have also performed variable temperature neutron diffraction on ammonium borodeuteride, ND$_{4}$BD$_{4}$, and report the full structural characterisation of the three phases identified as a result of these measurements. Furthermore, variable temperature inelastic neutron scatting (INS) measurements were performed on ammonia borane, NH$_{3}$BH$_{3}$, and the results are discussed in terms of crystallographic phase changes.

This thesis investigates the structure and thermal behaviour of LiBH4, NaBH4, KBH4, LiK(BH4)2, Ca(BH4)2 and Sr(BH4)2. LiK(BH4)2 is the first mixed alkali metal borohydride and was synthesised and characterised during this work. The crystal structures of these borohydrides were studied using variable temperature neutron and synchrotron X-ray diffraction. The synthesis of isotopically enriched samples of 7Li11BD4, Li11BD4, Na11BD4 and K11BD4 allowed high quality neutron diffraction data to be collected. Particular attention was paid to the exact geometry of the borohydride ions which were generally found to be perfect tetrahedra but with orientational disorder. New structures of Ca(BH4)2 were identified and the first crystal structure of Sr(BH4)2 was determined from synchrotron X-ray diffraction data. Solid state 11B NMR and Raman spectroscopy provided further information about the structure of these borohydrides. The thermal behaviour of the borohydrides was investigated using thermogravimetric analysis with mass spectrometry of the decomposition gas products. Hydrogen is the main decomposition gas product from all of these compounds but small amounts of B2H6 and BH3 were also detected during decomposition. Thermogravimetic analyses of Na11BD4 and K11BD4 were completed whilst collecting in-situ neutron diffraction data allowing information about structural changes and mass losses to be combined in order to better understand the decomposition process.

Hydrogen storage in lightweight hydrides continues to attract significant interest as the lack of a safe and efficient storage of hydrogen remains the major technological barrier to the widespread use of hydrogen as a fuel. The metal borohydrides Ca(BH₄)₂ and LiBH₄ form the subject of this thesis; three aspects of considerable academic interest were investigated by density functional theory (DFT) and molecular dynamics (MD) modelling. (i) High-pressure crystal structures of Ca(BH₄)₂ were predicted from a structural analogy between metal borohydrides and isoelectronic metal oxides. The structural stability of hydrogen storage materials under high pressure is an important aspect, as high-pressure polymorphs may provide structures with better hydrogen desorption properties. The isoelectronic analogue of Ca(BH₄)₂ is TiO₂, and structural equivalents of Ca(BH₄)₂ in the baddeleyite, columbite and cotunnite structures of TiO₂ were found to be stable at elevated pressure. Thermodynamic stability was evaluated by computing the Gibbs energy with respect to pressure and temperature. The pressure-dependence of the Helmholtz energy was determined to described a third-order Birch-Murnaghan equation of state, and the harmonic approximation was used to compute the vibrational energy levels and the Helmholtz energy as a function of temperature. The proposed structures are consistent with reports of two hitherto unidentified high-pressure phases observed experimentally. (ii) The disordered structure of the high-temperature phase of LiBH4 was studied by ab initio molecular dynamics (MD) at temperatures ranging from 200-535 K. It was found that the model emerging from analysis of the MD simulations properly accounts for dynamical disorder and fundamentally differs from the published experimental and theoretical structures. The validity of the MD model was corroborated by comparison of calculated pair distribution functions, vibrational spectra and a crystallographic model with neutron diffraction data; good agreement was found. A reassignment of the space group from P63mc to P63/mmc is proposed based on evidence for additional symmetry from MD simulations. (iii) Finally, a new MD-based method was developed to simulate fast ionic diffusion in LiBH₄. The colour diffusion algorithm - a nonequilibrium molecular dynamics method originally developed for the study of model fluids - was adapted and applied to self-diffusion of atoms in a solid for the first time. Calculated diffusion coefficients agreed very well with published measurements, and diffusion pathways that include collective particle effects were determined directly from the simulation results, thereby opening up a promising and efficient new method for the study of phenomena such as superionic conduction.

Ammonia borane and ammonium borohydride have been considered extensively as potential hydrogen storage materials. This thesis reports their structure and functional properties, emphasising the key role that dihydrogen bonding plays in both materials. The formation of a 'mobile phase' is considered to be the preliminary step in the decomposition of ammonia borane. The formation of this mobile phase has been studied using neutron diffraction, inelastic neutron spectroscopy and NMR. It has been found that in the mobile phase, 'end-to-end' flipping of the ammonia borane molecule occurs. This is an important precursor to the next step in the decomposition: the formation of the diammoniate of diborane. The dihydrogen bonding networks which occur in both the orthorhombic and the tetragonal phases of ammonia borane, and are the controlling factor in the decomposition process, were investigated using Density Functional Theory Molecular Dynamics (DFT-MD) simulations. It was hence shown that in the high-temperature tetragonal phase of ammonia borane, dihydrogen bonding is still an important stabilising interaction and there is little to distinguish between the three crystallographically distinct dihydrogen bonds. A closely related hydrogen storage material, ammonium borohydride, was also studied using the same techniques. Its low temperature phase progression was examined using variable temperature neutron diffraction. The vibrational modes of ammonium borohydride were assigned by comparing vibrational spectra determined using inelastic neutron spectroscopy with the results of DFT-MD simulations. Quasielastic neutron spectroscopy was used to show that both the ammonium and borohydride groups in ammonium borohydride perform discrete 'hopping' reorientational motions at a wide range of temperatures, and that the ammonium group has a mean residence time approximately 100 times less than that of the borohydride group. Hydrogen atom densities in the ammonium group were determined from DFT-MD simulations, and from refinements of high-resolution neutron diffraction data using cubic harmonic basis functions.