Theoretical study on the photodegradation reaction of deca-BDE in THF in the presence of furan

Pan, Lü; Zhang, Jia-Xu; Bian, Wensheng

doi:10.1007/s00214-015-1760-1

Cited by 2 publications

(1 citation statement)

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“…Pan and Bian applied LANL2DZ basis set augmented with polarization functions and diffuse functions for Br to study the photodegradation reaction for nona-BDEs with the solvent effect (methanol) [ 36 ]. Pan et al further adopted the above basis set for bromine to study the photodegradation reaction of BDE-209 in tetrahydrofuran (THF) [ 37 ]. In our previous studies, the pseudo-potential SDD basis set was used for Br atom and 6-31+G(d) basis set for C, H, O atoms to obtain molecular descriptors, which were used to predict the debromination rate constants for PBDEs in both gas-phase and solution [ 23 , 38 ].…”

Section: Introductionmentioning

confidence: 99%

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

Shi

et al. 2016

IJMS

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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.

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