Spin-flip reactions of Zr + C2H6 researched by relativistic density functional theory
| Autor: | Yi Xiao, Yi-Xiang Qiu, Xian-Yang Chen, Shu-Guang Wang |
|---|---|
| Rok vydání: | 2013 |
| Předmět: |
Exothermic reaction
Chemistry Organic Chemistry Catalysis Transition state Computer Science Applications Inorganic Chemistry Intersystem crossing Computational Theory and Mathematics Potential energy surface Atom Density functional theory Singlet state Physical and Theoretical Chemistry Atomic physics Natural bond orbital |
| Zdroj: | Journal of Molecular Modeling. 19:4003-4012 |
| ISSN: | 0948-5023 1610-2940 |
| DOI: | 10.1007/s00894-013-1932-7 |
| Popis: | 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 → 3 Zr-CH 3 -CH 3 ( 3 1) → 3 TS 1/2 → 3 ZrH-CH 2 -CH 3 ( 3 2) → 3 TS 2/3 ⟹ 1 ZrH2-CH2 = CH2 ( 1 3) → 1 TS 3/4 → 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. |
| Databáze: | OpenAIRE |
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