Investigation of spin-flip reactions of Zr + CH3CN by relativistic density functional theory.
J Phys Chem A
; 116(21): 5019-25, 2012 May 31.
Article
en En
| MEDLINE
| ID: mdl-22578173
ABSTRACT
To explore the details of the reaction mechanisms of Zr atoms with acetonitrile molecules, the triplet and singlet spin-state potential energy surfaces have been investigated. Density functional theory (DFT) with the relativistic zero-order regular approximation at the PW91/TZ2P level has been applied. The complicated minimum energy reaction path involves four transition states (TS), stationary states 1-5 and one spin inversion (indicated by â) (3)Zr + NCCH(3) â (3)Zr-η(1)-NCCH(3) ((3)1) â (3)TS(1/2) â (3)Zr-η(2)-(NC)CH(3) ((3)2) â (3)TS(2/3) â (3)ZrH-η(3)-(NCCH(2)) ((3)3) â (3)TS(3/4) â CNZrCH(3) ((3)4) â (1)TS(4/5) â CN(ZrH)CH(2) ((1)5). The minimum energy crossing point was determined with the help of the DFT fractional-occupation-number approach. The spin inversion leading from the triplet to the singlet state facilitates the activation of a C-H bond, lowering the rearrangement-barrier by 78 kJ/mol. The overall reaction is calculated to be exothermic by about 296 kJ/mol. All intermediate and product species were frequency and NBO analyzed. The species can be rationalized with the help of Lewis type formulas.
Texto completo:
1
Colección:
01-internacional
Base de datos:
MEDLINE
Idioma:
En
Revista:
J Phys Chem A
Asunto de la revista:
QUIMICA
Año:
2012
Tipo del documento:
Article
País de afiliación:
China