Electronic Properties and Ionic Photodissociation of Thionitrite Compounds. Photoelectron Spectroscopy and Vacuum Ultraviolet Synchrotron Study on RSNO [R= (CH3)2CH? and (CH3)3C?]

CANNEVA, ANTONELA; CAVASSO FILHO, REINALDO; ROMANO, ROSANA MARIEL; DELLA VÉDOVA, CARLOS OMAR; TONG, S.; GE, MAO-FA; ERBEN, MAURICIO FEDERICO

ChemistrySelect

ChemPubSoc Europe and Wiley-VCH

Año: 2017 vol. 2 p. 2021 - 2027

The gas phase electronic properties of thionitrites (RSNO) in both the outermost (valence) and the shallow-core regions (S 2p) are experimentally studied for the first time by using photoelectron spectroscopy and synchrotron radiation in the VUV range with time-of-flight mass spectrometry in the Photoelectron Photoion Coincidence (PEPICO) mode. The He(I)photoelectron spectrum of tert-butyl thionitrite, (CH3)3CSNO,has been recorded and analyzed with the assistance ofquantum chemical calculations. Furthermore, the dissociative photoionization mechanisms for two close related secondary and tertiary species, namely iso-propyl thionitrite, (CH3)2HCSNO (I) and (CH3)3CSNO (II), have been determined irradiating gaseous beams with photons in the 155?185 eV range, i. e. exciting and ionizing S 2p electrons of the central ?SNO group. The branching ratio of ions produced on this way is analyzed allowing for a clear description of the main fragmentationchannels operating after the electronic decay.