Spin-flip reactions of Zr + C2H6 researched by relativistic density functional theory.
J Mol Model
; 19(9): 4003-12, 2013 Sep.
Article
en En
| MEDLINE
| ID: mdl-23851999
Density functional theory (DFT) with relativistic corrections of zero-order regular approximation (ZORA) has been applied to explore the reaction mechanisms of ethane dehydrogenation by Zr atom with triplet and singlet spin-states. Among the complicated minimum energy reaction path, the available states involves three transition states (TS), and four stationary states (1) to (4) and one intersystem crossing with spin-flip (marked by -->): (3) Zr + C 2 H 6 â (3) Zr-CH 3 -CH 3 ((3)1) â (3)TS 1/2 â (3) ZrH-CH 2 -CH 3 ((3)2) â (3) TS 2/3 --> (1) ZrH2-CH2 = CH2 ((1) 3) â (1) TS 3/4 â (1) ZrH 3 -CH = CH 2 ((1)4). The minimum energy crossing point is determined with the help of the DFT fractional-occupation-number (FON) approach. The spin inversion leads the reaction pathway transferring from the triplet potential energy surface (PES) to the singlet's accompanying with the activation of the second C-H bond. The overall reaction is calculated to be exothermic by about 231 kJ mol(-1). Frequency and NBO analysis are also applied to confirm with the experimental observed data.
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1
Colección:
01-internacional
Base de datos:
MEDLINE
Idioma:
En
Revista:
J Mol Model
Asunto de la revista:
BIOLOGIA MOLECULAR
Año:
2013
Tipo del documento:
Article
País de afiliación:
China