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Int. J. Mol. Sci. 2016, 17(6), 927; doi:10.3390/ijms17060927

Theoretical Studies on Structures, Properties and Dominant Debromination Pathways for Selected Polybrominated Diphenyl Ethers

1
Guizhou Provincial Key Laboratory for Information System of Mountainous Areas and Protection of Ecological Environment, Guizhou Normal University, Guiyang 550001, China
2
Department of Applied Chemistry, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China
*
Author to whom correspondence should be addressed.
Academic Editor: Marie-Christine Bacchus
Received: 20 April 2016 / Revised: 1 June 2016 / Accepted: 3 June 2016 / Published: 16 June 2016
(This article belongs to the Section Physical Chemistry, Theoretical and Computational Chemistry)
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Abstract

The B3LYP/6-311+G(d)-SDD method, which considers the relativistic effect of bromine, was adopted for the calculations of the selected polybrominated diphenyl ethers (PBDEs) in the present study, in which the B3LYP/6-311+G(d) method was also applied. The calculated values and experimental data for structural parameters of the selected PBDEs were compared to find the suitable theoretical methods for their structural optimization. The results show that the B3LYP/6-311+G(d) method can give the better results (with the root mean square errors (RMSEs) of 0.0268 for the C–Br bond and 0.0161 for the C–O bond) than the B3LYP/6-311+G(d)-SDD method. Then, the B3LYP/6-311+G(d) method was applied to predict the structures for the other selected PBDEs (both neutral and anionic species). The lowest unoccupied molecular orbital (LUMO) and the electron affinity are of a close relationship. The electron affinities (vertical electron affinity and adiabatic electron affinity) were discussed to study their electron capture abilities. To better estimate the conversion of configuration for PBDEs, the configuration transition states for BDE-5, BDE-22 and BDE-47 were calculated at the B3LYP/ 6-311+G(d) level in both gas phase and solution. The possible debromination pathway for BDE-22 were also studied, which have bromine substituents on two phenyl rings and the bromine on meta-position prefers to depart from the phenyl ring. The reaction profile of the electron-induced reductive debromination for BDE-22 were also shown in order to study its degradation mechanism. View Full-Text
Keywords: relativistic effects; debromination; pseudo-potentials; transition state; adiabatic electron affinity; vertical electron affinity relativistic effects; debromination; pseudo-potentials; transition state; adiabatic electron affinity; vertical electron affinity
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Li, L.; Hu, J.; Shi, X.; Ruan, W.; Luo, J.; Wei, X. Theoretical Studies on Structures, Properties and Dominant Debromination Pathways for Selected Polybrominated Diphenyl Ethers. Int. J. Mol. Sci. 2016, 17, 927.

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