Ricerc@Sapienza

The photoionization dynamics of OsO4 and RuO4, chosen as model systems of small-size mononuclear heavy-metal complexes, has been theoretically studied by the time-dependent density functional theory (TDDFT). Accurate experimental measurements of photoionization dynamics as a benchmarking test for the theory are reported for the photoelectron asymmetry parameters of outer valence ionizations of OsO4, measured in the 17-90 eV photon energy range. The theoretical results are in good agreement with the available experimental data.

The effect of intermolecular H-bonding interactions on the local electronic structure of N-containing functional groups (amino group and pyridine-like N) that are characteristic of polymeric carbon nitride materials p-CN(H), a new class of metal-free organophotocatalysts, was investigated. Specifically, the melamine molecule, a building block of p-CN(H), was characterized by X-ray photoelectron (XPS) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. The molecule was studied as a noninteracting system in the gas phase and in the solid state within a H-bonded network.

Preparing an anatase TiO2(101) surface with a high density of oxygen vacancies and associated reduced Ti species in the near-surface region results in drastic changes in the water adsorption chemistry compared to adsorption on a highly stoichiometric surface. Using synchrotron radiation excited photoelectron spectroscopy, we observe a change in the water growth mode, from layer-by-layer growth on the highly stoichiometric surface to bilayer growth on the reduced surface. Furthermore, we have been able to observe Ti3+ enrichment at the surface upon water adsorption.

The anatase TiO2(101) surface and its interaction with water is an important topic in oxide surface chemistry. Firstly, it benchmarks the properties of the majority facet of TiO2 nanoparticles and, secondly, there is a controversy as to whether the water molecule adsorbs intact or deprotonates. We have addressed the adsorption of water on anatase TiO2(101) by synchrotron radiation photoelectron spectroscopy. Three two-dimensional water structures are found during growth at different temperatures: at 100 K, a metastable structure forms with no hydrogen bonding between the water molecules.

The C, N and O 1s excitation and ionization processes of 5X-uracil (X = F, Cl, Br, and I) were investigated using near edge X-ray absorption fine structure (NEXAFS) and X-ray photoemission (XPS) spectroscopies. This study aims at the fine assessment of the effects of the functionalization of uracil molecules by halogen atoms having different electronegativity and bound to the same molecular site. Two DFT-based approaches, which rely on different paradigms, have been used to simulate the experimental spectra and to assign the corresponding features.

The initial deactivation pathways of gaseous 2-nitrophenol excited at 268 nm were investigated by time-resolved photoelectron spectroscopy (TRPES) with femtosecond-VUV light, produced by a monochromatized High Harmonic Generation source. TRPES allowed us to obtain new, valuable experimental information about the ultrafast excited-state dynamics of 2-nitrophenol in the gas phase.

Metal halide perovskites have emerged as materials of high interest for solar energy-to-electricity conversion, and in particular, the use of mixed-ion structures has led to high power conversion efficiencies and improved stability. For this reason, it is important to develop means to obtain atomic level understanding of the photoinduced behavior of these materials including processes such as photoinduced phase separation and ion migration.