| The material presented here can be divided into two categories, (i) chemistry of energetic materials, or (ii) interfacial quantum chemistry. The work in Chapters 2 and 3 was performed as part of a program to simulate accidental fires and explosions. Combustion simulations rely on a great deal of chemical information such as enthalpy changes and reaction barriers for hundreds of chemical reactions, and Chapter 2 proposes a strategy for efficient calculation of these parameters. Also important in the simulation of combustion is the ability to track physical properties through phase changes. Chapter 3 emphasizes the importance of polarization in the crystal phase of DMNA; this knowledge is vital to the development of accurate molecular dynamics force fields for simulating thermophysical properties of explosive materials.; Chapters 4, 5, and 6, are devoted to forefront theoretical research in the field of interfacial chemistry. As an example of chemistry at the solid-vacuum interface, the catalytic production of methyl radicals over lithium-doped magnesium oxide is considered. A new mechanism is proposed for the catalytic coupling of methane that is more consistent with available experimental data than the previously proposed Ito-Lunsford mechanism. The final two chapters describe in great detail the interactions of water with the magnesium oxide (100) surface. Applied is a novel theoretical approach that combines an embedded quantum cluster for modeling the crystal surface with a dielectric continuum representation of the solution phase. Validation of this approach is achieved by demonstrating that it can reasonably model complicated many-body interactions at solid-liquid interfaces. Attention is then focused on the challenging problem regarding the chemical reactivity of the MgO-water interface. Presented are both experimental and theoretical studies that provide new evidence for dissociative chemisorption of water molecules at the MgO(100) interface with bulk water. These results provide a significant contribution to the understanding of oxide-water interfaces. |
