The dissociation of the 4-chlorotoluene radical anion, in the corresponding arylic open-shell and chloride closed-shell species, has been studied using semiempirical and ab initio methods, in both cases ROHF and UHF calculations have been performed. It is shown that semiempirical PESs are not reliable. While, at least a 3-21g basis set is needed to obtain an ab initio single determinant global dissociative path (which is qualitatively consistent with the experimental evidence). In addition, UMP2, ROMP2, SOCI dissociative PESs are discussed, suggesting that ROHF-based methods are preferable to UHF-based ones. This is shown to depend on the spin contamination affecting the UHF wavefunction.

Theoretical study of the dissociative process of the 4-chlorotoluene radical anion / Fontanesi, Claudio. - In: JOURNAL OF MOLECULAR STRUCTURE. THEOCHEM. - ISSN 0166-1280. - 392:(1997), pp. 87-94.

Theoretical study of the dissociative process of the 4-chlorotoluene radical anion

FONTANESI, Claudio
1997-01-01

Abstract

The dissociation of the 4-chlorotoluene radical anion, in the corresponding arylic open-shell and chloride closed-shell species, has been studied using semiempirical and ab initio methods, in both cases ROHF and UHF calculations have been performed. It is shown that semiempirical PESs are not reliable. While, at least a 3-21g basis set is needed to obtain an ab initio single determinant global dissociative path (which is qualitatively consistent with the experimental evidence). In addition, UMP2, ROMP2, SOCI dissociative PESs are discussed, suggesting that ROHF-based methods are preferable to UHF-based ones. This is shown to depend on the spin contamination affecting the UHF wavefunction.
392
87
94
Theoretical study of the dissociative process of the 4-chlorotoluene radical anion / Fontanesi, Claudio. - In: JOURNAL OF MOLECULAR STRUCTURE. THEOCHEM. - ISSN 0166-1280. - 392:(1997), pp. 87-94.
Fontanesi, Claudio
File in questo prodotto:
Non ci sono file associati a questo prodotto.
Pubblicazioni consigliate

Licenza Creative Commons
I metadati presenti in IRIS UNIMORE sono rilasciati con licenza Creative Commons CC0 1.0 Universal, mentre i file delle pubblicazioni sono rilasciati con licenza Attribuzione 4.0 Internazionale (CC BY 4.0), salvo diversa indicazione.
In caso di violazione di copyright, contattare Supporto Iris

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11380/9028
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 28
  • ???jsp.display-item.citation.isi??? 21
social impact