Study of the termination of two acrylonitrile radicals and infrared spectrum

Li, X. and Yang, M.-S. and Xu, C. and Song, P-A. ORCID: and Chen, L. and Du, H.-C. and Wang, Y. (2014) Study of the termination of two acrylonitrile radicals and infrared spectrum. Spectroscopy and Spectral Analysis, 34 (9). pp. 2331-2336. ISSN 1000-0593


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.

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Item Type: Article (Commonwealth Reporting Category C)
Refereed: Yes
Item Status: Live Archive
Additional Information: Files associated with this item cannot be displayed due to copyright restrictions.
Faculty/School / Institute/Centre: No Faculty
Faculty/School / Institute/Centre: No Faculty
Date Deposited: 29 May 2017 05:53
Last Modified: 29 May 2017 05:53
Uncontrolled Keywords: Density Functional Theory (DFT); electronic structure; IR spectra; reaction mechanism; acrylonitrile monomers; guiding significances
Fields of Research (2008): 04 Earth Sciences > 0401 Atmospheric Sciences > 040199 Atmospheric Sciences not elsewhere classified
Fields of Research (2020): 37 EARTH SCIENCES > 3701 Atmospheric sciences > 370199 Atmospheric sciences not elsewhere classified
Socio-Economic Objectives (2008): D Environment > 96 Environment > 9602 Atmosphere and Weather > 960202 Atmospheric Processes and Dynamics
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