Study of the termination of two acrylonitrile radicals and infrared spectrum
Article
Article Title | Study of the termination of two acrylonitrile radicals and infrared spectrum |
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Article Category | Article |
Authors | Li, X. (Author), Yang, M.-S. (Author), Xu, C. (Author), Song, P-A. (Author), Chen, L. (Author), Du, H.-C. (Author) and Wang, Y. (Author) |
Journal Title | Spectroscopy and Spectral Analysis |
Journal Citation | 34 (9), pp. 2331-2336 |
Number of Pages | 6 |
Year | 2014 |
Place of Publication | China |
Digital Object Identifier (DOI) | https://doi.org/10.3964/j.issn.1000-0593(2014)09-2331-06 |
Web Address (URL) | http://d.wanfangdata.com.cn/Periodical/gpxygpfx201409004 |
Abstract | By using the density functional theory, the study of reaction termination mechanism of two (CH3)2(CN)C-CH2-(CN)CH was carried out at the B3LYP/6-31G(d) level. The initiator AIBN was used. Reactants, coupled intermediates, transition states and disproportionation products were optimized at the B3LYP/6-31G(d) level. Then the total energies corrected by zero-point energy, vibrational frequencies and electronic structures were calculated, the transition states structure was also verified. The results show that it forms the energy-rich adducts a through the coupling termination. Then, the disproportionation product P[p1(CH3)2(CN) C-CH=CHCN+p2 (CH3)2(CN)C-CH2-CH2CN] formed via hydrogen shift and dissociation. The reactions of coupling termination and disproportionation termination are all exothermic reactions, and the coupled product has lower energy. The rate constant of step a→TS→P is k(298.15 K)=2.71×10-59 at the normal atmospheric temperature. Disproportionation termination occurs more easily with the reaction temperature rising, so the proportion of disproportionation products is increasing. Also, the analysis of infrared spectrogram of each species in reaction process shows chemical change of free radicals in the whole termination reaction. The authors give the HOMO-LUMO in this paper to verify the accuracy of biradical coupling termination and structures. It has important guiding significance to controlling the free radicals termination methods of acrylonitrile monomer. |
Keywords | Density Functional Theory (DFT); electronic structure; IR spectra; reaction mechanism; acrylonitrile monomers; guiding significances |
Contains Sensitive Content | Does not contain sensitive content |
ANZSRC Field of Research 2020 | 370199. Atmospheric sciences not elsewhere classified |
Public Notes | Files associated with this item cannot be displayed due to copyright restrictions. |
Byline Affiliations | Zhejiang A & F University, China |
Lanzhou University, China | |
Institution of Origin | University of Southern Queensland |
https://research.usq.edu.au/item/q4126/study-of-the-termination-of-two-acrylonitrile-radicals-and-infrared-spectrum
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