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Electronic Properties and Ionic Photodissociation of Thionitrite Compounds RSNO [R=(CH 3 ) 3 C– and (CH 3 ) 2 CH–]
Author(s) -
Cánneva Antonela,
Filho Reinaldo L. Cavasso,
Romano Rosana M.,
Della Védova Carlos O.,
Tong Shengrui,
Ge Maofa,
Erben Mauricio F.
Publication year - 2017
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201602002
Subject(s) - photoionization , x ray photoelectron spectroscopy , ionic bonding , valence electron , chemistry , photodissociation , atomic physics , ion , fragmentation (computing) , valence (chemistry) , photoemission spectroscopy , branching fraction , mass spectrometry , electronic structure , electron , electron spectroscopy , analytical chemistry (journal) , ionization , photochemistry , physics , computational chemistry , nuclear physics , nuclear magnetic resonance , organic chemistry , operating system , chromatography , computer science
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, (CH 3 ) 3 CSNO, has been recorded and analyzed with the assistance of quantum chemical calculations. Furthermore, the dissociative photoionization mechanisms for two close related secondary and tertiary species, namely iso ‐propyl thionitrite, (CH 3 ) 2 HCSNO ( I ) and (CH 3 ) 3 CSNO ( 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 fragmentation channels operating after the electronic decay.