Studies of pure rotational spectra of isolated molecules and molecular adducts using pulsed jet Fourier transform microwave (PJ-FTM) spectroscopy

This thesis focuses on studying molecular structure and internal dynamics by using pulsed jet Fourier transform microwave (PJ-FTMW) spectroscopy combined with theoretical calculations. Several kinds of interesting chemical problems are investigated by analyzing the MW spectra of the corresponding molecular systems. First, the general aspects of rotational spectroscopy are summarized, and then the basic theory on molecular rotation and experimental method are described briefly. ab initio and density function theory (DFT) calculations that used in this thesis to assist the assignment of rotational spectrum are also included. From chapter 3 to chapter 8, several molecular systems concerning different kind of general chemical problems are presented. In chapter 3, the conformation and internal motions of dimethyl sulfate are reported. The internal rotations of the two methyl groups split each rotational transition into several components line, allowing for the determination of accurate values of the V3 barrier height to internal rotation and of the orientation of the methyl groups with respect to the principal axis system. In chapter 4 and 5, the results concerning two kinds of carboxylic acid bi-molecules, formed via two strong hydrogen bonds, are presented. This kind of adduct is interesting also because a double proton transfer can easily take place, connecting either two equivalent or two non-equivalent molecular conformations. Chapter 6 concerns a medium strong hydrogen bonded molecular complex of alcohol with ether. The dimer of ethanol-dimethylether was chosen as the model system for this purpose. Chapter 7 focuses on weak halogen…H hydrogen bond interaction. The nature of O-H…F and C-H…Cl interaction has been discussed through analyzing the rotational spectra of CH3CHClF/H2O. In chapter 8, two molecular complexes concerning the halogen bond interaction are presented.

Deposition of thin films by a non-equilibrium atmospheric pressure Plasma Jet: a poly-diagnostic study

The use of atmospheric pressure plasmas for thin film deposition on thermo-sensitive materials is currently one of the main challenges of the plasma scientific community. Despite the growing interest in this field, the existing knowledge gap between gas-phase reaction mechanisms and thin film properties is still one of the most important barriers to overcome for a complete understanding of the process. In this work, thin films surface characterization techniques, combined with passive and active gas-phase diagnostic methods, were used to provide a comprehensive study of the Ar/TEOS deposition process assisted by an atmospheric pressure plasma jet. SiO2-based thin films exhibiting a well-defined chemistry, a good morphological structure and high uniformity were studied in detail by FTIR, XPS, AFM and SEM analysis. Furthermore, non-intrusive spectroscopy techniques (OES, filter imaging) and laser spectroscopic methods (Rayleigh scattering, LIF and TALIF) were employed to shed light on the complexity of gas-phase mechanisms involved in the deposition process and discuss the influence of TEOS admixture on gas temperature, electron density and spatial-temporal behaviours of active species. The poly-diagnostic approach proposed in this work opens interesting perspectives both in terms of process control and optimization of thin film performances.

Cross-population radio galaxies as a test of the jet-accretion relationship

Radio galaxies (RGs) are extremely relevant in addressing important unknowns concerning the interaction among black hole accretion, radio jets, and the environment. In the classical scheme, their accretion rate and ejection of relativistic jets are directly linked: efficient accretion (HERG) is associated with powerful edge-brightened jets (FRIIs); inefficient accretion (LERG) is associated with weak edge-darkened jets (FRIs). The observation of RGs with an inefficient engine associated with edge-brightened radio emission (FRII-LERGs) broke this scheme. FRII-LERGs constitute a suitable population to explore how accretion and ejection are linked and evaluate the environment's role in shaping jets. To this aim, we performed a multiwavelength study of different RGs catalogs spanning from Jy to mJy flux densities. At first, we investigated the X-ray properties of a sample of 51 FRIIs belonging to the 3CR catalog at z<0.3. Two hypotheses were invoked to explain FRII-LERGs behavior: evolution from classical FRIIs; the role of the environment. Next, we explored the mJy sky by studying the optical-radio properties of hundreds of RGs at z<0.15 (Best & Heckman 2012 sample). FRII-LERGs appear more similar to the old FRI-LERGs than to the young FRII-HERGs. These results point towards an evolutive scenario, however, nuclear time scale changes, star population aging, and kpc-Mpc radio structure modification do not agree. The role of the Mpc environment was then investigated. The Wen et al. 2015 galaxy clusters sample, built exploiting the SDSS survey, allowed us to explore the habitat of 7219 RGs at z<0.3. Most RGs are found to live in outside clusters. For these sources, differences among RG classes are still present. Thus, the environment is not the key parameter, and the possibility of intrinsic differences was reconsidered: we speculated that different black hole properties (spin and magnetic field at its horizon) could determine the observed spread in jet luminosity.