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.

Ab-initio study of hydrogen technology materials for hydrogen storage and proton conduction

This dissertation deals with two specific aspects of a potential hydrogen-based energy economy, namely the problems of energy storage and energy conversion. In order to contribute to the solution of these problems, the structural and dynamical properties of two promising materials for hydrogen storage (lithium imide/amide) and proton conduction (poly[vinyl phosphonic acid]) are modeled on an atomistic scale by means of first principles molecular dynamics simulation methods.rnrnrnIn the case of the hydrogen storage system lithium amide/imide (LiNH_2/Li_2NH), the focus was on the interplay of structural features and nuclear quantum effects. For these calculations, Path-Integral Molecular Dynamics (PIMD) simulations were used. The structures of these materials at room temperature were elucidated; in collaboration with an experimental group, a very good agreement between calculated and experimental solid-state 1H-NMR chemical shifts was observed. Specifically, the structure of Li_2NH features a disordered arrangement of the Li lattice, which was not reported in previous studies. In addition, a persistent precession of the NH bonds was observed in our simulations. We provide evidence that this precession is the consequence of a toroid-shaped effective potential, in which the protons in the material are immersed. This potential is essentially flat along the torus azimuthal angle, which might lead to important quantum delocalization effects of the protons over the torus.rnrnOn the energy conversion side, the dynamics of protons in a proton conducting polymer (poly[vinyl phosphonic acid], PVPA) was studied by means of a steered ab-initio Molecular Dynamics approach applied on a simplified polymer model. The focus was put on understanding the microscopic proton transport mechanism in polymer membranes, and on characterizing the relevance of the local environment. This covers particularly the effect of water molecules, which participate in the hydrogen bonding network in the material. The results indicate that these water molecules are essential for the effectiveness of proton conduction. A water-mediated Grotthuss mechanism is identified as the main contributor to proton conduction, which agrees with the experimentally observed decay on conductivity for the same material in the absence of water molecules.rnrnThe gain in understanding the microscopic processes and structures present in this materials can help the development of new materials with improved properties, thus contributing to the solution of problems in the implementation of fuel cells.

La lingua e l'estraneità: Franco Biondi e la letteratura dell'immigrazione in Germania. Proposta di traduzione di "Und nun schieben sie mich ab"

In questo lavoro è presentata una proposta di traduzione del racconto Und nun schieben sie mich ab (Biondi, 1985: 168- 174), di Franco Biondi, un autore di origini italiane residente in Germania dal 1965 (Amodeo, 2007: 6). Data la sua biografia, Biondi è un autore emblematico tanto della letteratura italiana della migrazione, quanto della letteratura dell’immigrazione in Germania, a testimonianza di come questa letteratura sia riuscita a superare i confini letterari nazionali per entrare a far parte di una «letteratura mondiale della transculturalità» (Amodeo, 2000: 327) . Considerati il terreno comune su cui si sono sviluppate le opere di autori di varie nazionalità in Germania, e l’eterogeneità dei contesti letterari e sociali degli autori italiani nei vari Paesi, si è ritenuto più efficace focalizzare i capitoli teorici del lavoro sulla letteratura dell’immigrazione in Germania, con un’attenzione particolare agli autori di origine italiana. La proposta di traduzione sarà preceduta da un inquadramento storico degli albori della letteratura dell’immigrazione in Germania, nata negli anni Sessanta del Novecento. Da lì si procederà presentando gli sviluppi di questa letteratura fino agli anni più recenti: si partirà dalla letteratura dell’immigrazione in Germania prodotta da autori di varie nazionalità, entrando poi nel merito degli autori di origine italiana attivi in Germania. Il terzo capitolo è dedicato a Franco Biondi, di cui saranno presentate una breve biografia e le opere più significative. Il quarto e il quinto capitolo sono dedicati interamente al racconto Und nun schieben sie mich ab (Biondi, 1985): in particolare, il quarto capitolo contiene un’analisi del tema e del contenuto del racconto, contestualizzato poi all’interno della raccolta “Passavantis Rückkehr” (Ibid.) e dell’opera dell’autore; in questo capitolo inoltre viene presentata un’analisi linguistica e stilistica del racconto. Il quinto capitolo contiene la proposta di traduzione, seguita da un commento della traduzione e delle strategie utilizzate.

Excited state properties of formamide in water solution: An ab initio study

We present ab initio quantum calculation of the optical properties of formamide in vapor phase and in water solution. We employ time dependent density functional theory for the isolated molecule and many-body perturbation theory methods for the system in solution. An average over several molecular dynamics snapshots is performed to take into account the disorder of the liquid. We find that the excited stateproperties of the gas-phase formamide are strongly modified by the presence of the water solvent: the geometry of the molecule is distorted and the electronic and optical properties are severely modified. The important interaction among the formamide and the water molecules forces us to use fully quantum methods for the calculation of the excited stateproperties of this system. The excitonic wave function is localized both on the solute and on part of the solvent.