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.

Gas phase ion chemistry has fundamental and applicative purposes since it allows the study of the chemical processes in a solvent free environment and represents models for reactions occurring in the space at low and high temperatures. In this work the ion-molecule reaction of sulfur dioxide ion SO.+2 with carbon monoxide CO is investigated in a joint experimental and theoretical study.

SO2 has been proposed in solar geoengineering as a precursor of H2SO4 aerosol, a cooling agent active in the stratosphere to contrast climate change. Atmospheric ionization sources can ionize SO2 into excited states of (Formula presented.), which quickly reacts with trace gases in the stratosphere. In this work we explore the reaction of (Formula presented.) with (Formula presented.) excited by tunable synchrotron radiation, leading to (Formula presented.) ((Formula presented.)), where H contributes to O3 depletion and OH formation.

In this work an experimental and theoretical study on the formation of HSO2 + ion from the SO2 ?++CH4 and SO2 ?++H2O ion–molecule reactions at different temperatures is reported. Tunable synchrotron radiation was used to produce the SO2 ?+ ion in excited ro-vibrational levels of the ionic ground state X2A1 and mass spectrometry was employed to identify the product ions. Calculations in the frame of the density functional theory and variational transition state theory were combined to explore the dynamics of the reactions.

The fragmentation of ClNO upon resonant core-electron excitation to the LUMO and LUMO+1 orbitals at the N and O K-edges is investigated. The produced fragment ions were detected in coincidence with a position sensitive ion time-of-flight detector which enables deduction of the angular distribution of the ions. This facilitates a comparison between the two resonances and the two K-edges with respect to fragmentation time, transition dipole moment orientation, fragment yield of single-ion and ion-pair channels, and fragmentation mechanisms.

Propylene oxide, a favorite target of experimental and theoretical studies of circular dichroism, was recently discovered in interstellar space, further amplifying the attention to its role in the current debate on protobiological homochirality.

A photoelectron-photoion-photoion coincidence technique, using an ion imaging detector and tunable synchrotron radiation in the 18.0-37.0 eV photon energy range, inducing the ejection of molecular valence electrons, has been applied to study the double ionization of the propylene oxide, a simple prototype chiral molecule. The experiment performed at the Elettra Synchrotron Facility (Trieste, Italy) allowed to determine angular distributions for ions produced by the two-body dissociation reactions following the Coulomb explosion of the intermediate (C3H6O)(2+) molecular dication.

An experimental investigation on the fragmentation dynamics following the double photoionization of simple organic molecules of astrochemical interest, propylene oxide and N-methylformamide molecules, induced by VUV photons has been reported. Experiments used linearly polarized light in the 18-37 eV (propylene oxide) and 26-45 eV (N-methylformamide) photon energy range at the ELETTRA Synchrotron Facility of Trieste (Italy), coupling ion imaging and electron-ion-ion coincidence techniques with time-of-flight mass spectrometry.