Electronic Properties and Ionic Photodissociation of Thionitrite Compounds RSNO [R = (CH3)3C? and (CH3)2CH?]

ANTONELA CANNEVA; REINALDO L. CAVASSO FILHO; ROSANA M. ROMANO; CARLOS O. DELLA VÉDOVA; SHENGRUI TONG; MAOFA GE; MAURICIO F. ERBEN

Chemistry SELECT

Wiley-VCH

Año: 2017 vol. 2 p. 2021 - 2027

The gas phase electronic properties of thionitrites (RSNO) inboth the outermost (valence) and the shallow-core regions (S2p) are experimentally studied for the first time by usingphotoelectron spectroscopy and synchrotron radiation in theVUV range with time-of-flight mass spectrometry in the PhotoelectronPhotoion 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 dissociativephotoionization mechanisms for two close related secondaryand tertiary species, namely iso-propyl thionitrite, (CH3)2HCSNO(I) and (CH3)3CSNO (II), have been determined irradiatinggaseous 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 analyzedallowing for a clear description of the main fragmentationchannels operating after the electronic decay.