Ab initio quantum mechanical investigation of structural and chemical-physical properties of selected minerals for minero-petrological, structural ceramic and biomaterial applications

The purpose of this thesis is the atomic-scale simulation of the crystal-chemical and physical (phonon, energetic) properties of some strategically important minerals for structural ceramics, biomedical and petrological applications. These properties affect the thermodynamic stability and rule the mineral-environment interface phenomena, with important economical, (bio)technological, petrological and environmental implications. The minerals of interest belong to the family of phyllosilicates (talc, pyrophyllite and muscovite) and apatite (OHAp), chosen for their importance in industrial and biomedical applications (structural ceramics) and petrophysics. In this thesis work we have applicated quantum mechanics methods, formulas and knowledge to the resolution of mineralogical problems ("Quantum Mineralogy”). The chosen theoretical approach is the Density Functional Theory (DFT), along with periodic boundary conditions to limit the portion of the mineral in analysis to the crystallographic cell and the hybrid functional B3LYP. The crystalline orbitals were simulated by linear combination of Gaussian functions (GTO). The dispersive forces, which are important for the structural determination of phyllosilicates and not properly con-sidered in pure DFT method, have been included by means of a semi-empirical correction. The phonon and the mechanical properties were also calculated. The equation of state, both in athermal conditions and in a wide temperature range, has been obtained by means of variations in the volume of the cell and quasi-harmonic approximation. Some thermo-chemical properties of the minerals (isochoric and isobaric thermal capacity) were calculated, because of their considerable applicative importance. For the first time three-dimensional charts related to these properties at different pressures and temperatures were provided. The hydroxylapatite has been studied from the standpoint of structural and phonon properties for its biotechnological role. In fact, biological apatite represents the inorganic phase of vertebrate hard tissues. Numerous carbonated (hydroxyl)apatite structures were modelled by QM to cover the broadest spectrum of possible biological structural variations to fulfil bioceramics applications.

Spectral asymptotic properties of semi-regular non-commutative harmonic oscillators

The study carried out in this thesis is devoted to spectral analysis of systems of PDEs related also with quantum physics models. Namely, the research deals with classes of systems that contain certain quantum optics models such as Jaynes-Cummings, Rabi and their generalizations that describe light-matter interaction. First we investigate the spectral Weyl asymptotics for a class of semiregular systems, extending to the vector-valued case results of Helffer and Robert, and more recently of Doll, Gannot and Wunsch. Actually, the asymptotics by Doll, Gannot and Wunsch is more precise (that is why we call it refined) than the classical result by Helffer and Robert, but deals with a less general class of systems, since the authors make an hypothesis on the measure of the subset of the unit sphere on which the tangential derivatives of the X-Ray transform of the semiprincipal symbol vanish to infinity order. Abstract Next, we give a meromorphic continuation of the spectral zeta function for semiregular differential systems with polynomial coefficients, generalizing the results by Ichinose and Wakayama and Parmeggiani. Finally, we state and prove a quasi-clustering result for a class of systems including the aforementioned quantum optics models and we conclude the thesis by showing a Weyl law result for the Rabi model and its generalizations.