Electronic Properties and Dissociative Photoionization of Thiocyanates, Part III. The Effect of the Group’s Electronegativity in the Valence and Shallow-Core (Sulfur and Chlorine 2p) Regions of CCl<sub>3</sub>SCN and CCl<sub>2</sub>FSCN
Both photoelectron spectroscopy (PES) data and PhotoElectron-PhotoIon-Coincidence (PEPICO) spectra obtained from a synchrotron facility have been used to examine the electronic structure and the dissociative ionization of halomethyl thiocyantes in the valence and shallow-core S 2p and Cl 2pregions....
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| Autores principales: | , , , , , , , |
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| Formato: | Articulo |
| Lenguaje: | Inglés |
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2017
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| Acceso en línea: | http://sedici.unlp.edu.ar/handle/10915/107184 https://pubs.acs.org/doi/10.1021/acs.jpca.7b08395 |
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I19-R120-10915-107184 |
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dspace |
| institution |
Universidad Nacional de La Plata |
| institution_str |
I-19 |
| repository_str |
R-120 |
| collection |
SEDICI (UNLP) |
| language |
Inglés |
| topic |
Ciencias Exactas Química Thiocyanates electronic structure |
| spellingShingle |
Ciencias Exactas Química Thiocyanates electronic structure Rodríguez Pirani, Lucas Della Védova, Carlos Omar Geronés, Mariana Romano, Rosana Mariel Cavasso Filho, Reinaldo Ge, Maofa Ma, Chunping Erben, Mauricio Federico Electronic Properties and Dissociative Photoionization of Thiocyanates, Part III. The Effect of the Group’s Electronegativity in the Valence and Shallow-Core (Sulfur and Chlorine 2p) Regions of CCl<sub>3</sub>SCN and CCl<sub>2</sub>FSCN |
| topic_facet |
Ciencias Exactas Química Thiocyanates electronic structure |
| description |
Both photoelectron spectroscopy (PES) data and PhotoElectron-PhotoIon-Coincidence (PEPICO) spectra obtained from a synchrotron facility have been used to examine the electronic structure and the dissociative ionization of halomethyl thiocyantes in the valence and shallow-core S 2p and Cl 2pregions. Two simple and closely related molecules, namely, CCl<sub>3</sub>SCN and CCl<sub>2</sub>FSCN, have been analyzed to assess the role of halogen substitution in the electronic properties of thiocyanates. The assignment of the He(I) photoelectron spectra has been achieved with the help of quantum chemical calculations at the outer-valence Green’s function (OVGF) level of approximation. The first ionization energies observed at 10.55 and 10.78 eV for CCl<sub>3</sub>SCN and CCl<sub>2</sub>FSCN, respectively, are assigned to ionization processes from the sulfur lone pair orbital [n(S)]. When these molecules are compared with CX<sub>3</sub>SCN (X = H, Cl, F) species, a linear relationship between the vertical first ionization energy and electronegativity of CX<sub>3</sub> group is observed. Irradiation of CCl<sub>3</sub>SCN and CCl<sub>2</sub>FSCN with photons in the valence energy regions leads to the formation of CCl<sub>2</sub>X⁺ and CClXSCN⁺ ions (X = Cl or F). Additionally, the achievement of the fragmentation patterns and the total ion yield spectra obtained from the PEPICO data in the S 2p and Cl 2p regions and several dissociation channels can be inferred for the core-excited species by using the triple coincidence PEPIPICO (PhotoElectron-PhotoIon-PhotoIon-Coincidence) spectra. |
| format |
Articulo Articulo |
| author |
Rodríguez Pirani, Lucas Della Védova, Carlos Omar Geronés, Mariana Romano, Rosana Mariel Cavasso Filho, Reinaldo Ge, Maofa Ma, Chunping Erben, Mauricio Federico |
| author_facet |
Rodríguez Pirani, Lucas Della Védova, Carlos Omar Geronés, Mariana Romano, Rosana Mariel Cavasso Filho, Reinaldo Ge, Maofa Ma, Chunping Erben, Mauricio Federico |
| author_sort |
Rodríguez Pirani, Lucas |
| title |
Electronic Properties and Dissociative Photoionization of Thiocyanates, Part III. The Effect of the Group’s Electronegativity in the Valence and Shallow-Core (Sulfur and Chlorine 2p) Regions of CCl<sub>3</sub>SCN and CCl<sub>2</sub>FSCN |
| title_short |
Electronic Properties and Dissociative Photoionization of Thiocyanates, Part III. The Effect of the Group’s Electronegativity in the Valence and Shallow-Core (Sulfur and Chlorine 2p) Regions of CCl<sub>3</sub>SCN and CCl<sub>2</sub>FSCN |
| title_full |
Electronic Properties and Dissociative Photoionization of Thiocyanates, Part III. The Effect of the Group’s Electronegativity in the Valence and Shallow-Core (Sulfur and Chlorine 2p) Regions of CCl<sub>3</sub>SCN and CCl<sub>2</sub>FSCN |
| title_fullStr |
Electronic Properties and Dissociative Photoionization of Thiocyanates, Part III. The Effect of the Group’s Electronegativity in the Valence and Shallow-Core (Sulfur and Chlorine 2p) Regions of CCl<sub>3</sub>SCN and CCl<sub>2</sub>FSCN |
| title_full_unstemmed |
Electronic Properties and Dissociative Photoionization of Thiocyanates, Part III. The Effect of the Group’s Electronegativity in the Valence and Shallow-Core (Sulfur and Chlorine 2p) Regions of CCl<sub>3</sub>SCN and CCl<sub>2</sub>FSCN |
| title_sort |
electronic properties and dissociative photoionization of thiocyanates, part iii. the effect of the group’s electronegativity in the valence and shallow-core (sulfur and chlorine 2p) regions of ccl<sub>3</sub>scn and ccl<sub>2</sub>fscn |
| publishDate |
2017 |
| url |
http://sedici.unlp.edu.ar/handle/10915/107184 https://pubs.acs.org/doi/10.1021/acs.jpca.7b08395 |
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