Photoionization and photofragmentation study of ClC(O)OSO2CF3 in the valence-, inner-, and core-electrons energy regions.

ANGÉLICA MORENO BETANCOURT; BAVA YANINA BELÉN; BERRUETA MARTINEZ YANINA; CAVASSO FILHO R. L.; DELLA VÉDOVA CARLOS O.; ERBEN MAURICIO F.; GERONÉS MARIANA; ROMANO ROSANA M.

Campinas

Congreso; 23ª Reunião Anual de Usuários do LNLS/CNPEM Laboratório Nacional de Luz Síncrotron; 2013

Laboratorio Nacional de Luz Sincrotrón

Photoionization and photofragmentation study of ClC(O)OSO2CF3 in the valence-, inner-, and core-electrons energy regions.As part of a research project dedicated to the study of the electronic properties of molecules containing the SO2- group and halogen atoms, we present here the fragmentation studies following phoionization of valence, inner-shell and core-shell electrons of chlorocarbonyl trifluoromethanesulfonate, ClC(O)OSO2CF3. This compound has been prepared by our research group, and its conformational, structural and spectroscopic properties were studied using different experimental and theoretical techniques. Gas electron diffraction and vibrational analysis were interpreted in terms of an equilibrium of two conformers in the gas phase. ClC(O)OSO2CF3 was prepared by the reaction of ClC(O)SCl with AgOSO2CF3, according to the literature. The studies were performed using the experimental station for gaseous samples and coincidence techniques, in the TGM and SGM beamlines at LNLS. In the valence electron region, the PEPICO spectra are dominated by signals at m/q = 63/65 and 69, attributable to ClCO+ (with its characteristic isotopic splitting) and CF3+, respectively. If the gaseous sample is irradiated with synchrotron light of higher energies, several new fragments appear in the spectra, with an increasingimportance of atomic ions for ionization energies corresponding to core-shell electrons. SO2+, CF2+, SO+, CO2+, CF+, CO+, among others, are the fragment observed for irradiation energies in the region of S 2p and Cl 2p electrons, together with ClCO+ and CF3+. In the C 1s, O 1s and F 1s energy regions, atomic fragments became important in the spectra, being observable also signals originated in double charged species (CO2 2+, Cl2+, F2+, O2+, and C2+). The PEPIPICO spectra have revealed different photodissociation mechanisms. The most abundant islands in the spectra correspond to the formation of the following pairs of fragments in coincidence: ClCO+/CF3 +, S+/Cl+, and O+/S+, the fragmentation processes can be interpreted in terms of concerted mechanisms.