Electronic Properties and Ionic Photodissociation of Thionitrite Compounds RSNO [R=(CH<sub>3</sub>)<sub>3</sub>C– and (CH<sub>3</sub>)<sub>2</sub>CH–]
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 Pho...
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| Autores principales: | , , , , , , |
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| Formato: | Articulo |
| Lenguaje: | Inglés |
| Publicado: |
2017
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| Materias: | |
| Acceso en línea: | http://sedici.unlp.edu.ar/handle/10915/105936 https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/slct.201602002 |
| Aporte de: |
| Sumario: | 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 <i>tert</i>-butyl thionitrite, (CH<sub>3</sub>)<sub>3</sub>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 <i>iso</i>-propyl thionitrite, (CH<sub>3</sub>)<sub>2</sub>HCSNO (I) and (CH<sub>3</sub>)<sub>3</sub>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. |
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