Study of the termination of two acrylonitrile radicals and infrared spectrum

• Published in: Guang pu xue yu guang pu fen xi Vol. 34; no. 9; p. 2331
• Main Authors: Li, Xin, Yang, Meng-Shi, Xu, Can, Song, Ping-An, Chen, Liang, Du, Hong-Chen, Wang, Yu
• Format: Journal Article
• Language: Chinese
• Published: China 01.09.2014
• ISSN: 1000-0593
• DOI: 10.3964/j.issn.1000-0593(2014)09-2331-06

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 k(298.15 K) = 2.71 x 10(-59) at the normal atmospheric temperature. Disproportionation termination occurs more easily with t