Theoretical investigation on activation of CH and CC bonds of 2-butyne by gas-phase Nb atom
| Autor: | Zhe-Peng Deng, Yong-Cheng Wang, Pan-Pan Ma, Wen-Xue Wang, Shuang Li, Xiaoli Wang, Gui-Ping Niu, Yuwei Zhang |
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| Rok vydání: | 2016 |
| Předmět: |
Reaction mechanism
010405 organic chemistry Chemistry Spin–orbit interaction 010402 general chemistry Condensed Matter Physics 01 natural sciences Biochemistry Potential energy 0104 chemical sciences Catalysis Crystallography chemistry.chemical_compound Atom 2-Butyne Physical and Theoretical Chemistry Atomic physics Spin (physics) Doublet state |
| Zdroj: | Computational and Theoretical Chemistry. 1085:23-30 |
| ISSN: | 2210-271X |
| DOI: | 10.1016/j.comptc.2016.03.033 |
| Popis: | The spin-forbidden reaction mechanism of 2-butyne catalyzed by Nb atom has been systematically investigated on different potential energy surfaces (PESs) at the B3LYP level. Besides, spin inversion between surfaces of quartet and doublet states has been discussed by means of spin orbit coupling (SOC) calculations. The result indicates that there is a minimal energy crossing point (MECP) of two adiabatic surfaces in the process of the first C H bond activation. The values of P 1 ISC and P 2 ISC at MECP1 are 0.06 and 0.11, respectively. High probabilities near the crossing seam indicate that the reacting system will change its spin multiplicities from the quartet state to the doublet state. Finally, four H 2 elimination pathways and one CH 4 elimination pathway have been found, and the concerted H 2 -elimination, which leads to Nb(H 2 CCCCH 2 ) + H 2 , is the most favorable pathway. |
| Databáze: | OpenAIRE |
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