Theoretical Studies on Structures, Properties and Dominant Debromination Pathways for Selected Polybrominated Diphenyl Ethers | |
Li, Lingyun ; Hu, Jiwei ; Shi, Xuedan ; Ruan, Wenqian ; Luo, Jin ; Wei, Xionghui | |
刊名 | INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES |
2016 | |
关键词 | relativistic effects debromination pseudo-potentials transition state adiabatic electron affinity vertical electron affinity DENSITY-FUNCTIONAL THEORY REDUCTIVE DECHLORINATION ELECTRON-AFFINITIES TRANSITION-STATES AB-INITIO NANOPARTICLES DEGRADATION REACTIVITY KINETICS DIOXINS |
DOI | 10.3390/ijms17060927 |
英文摘要 | 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.; National Natural Science Foundation of China [21367009]; Government of Guizhou Province [LKS[2013]09]; SCI(E); PubMed; ARTICLE; lingyunli1989@126.com; jiweihu@yahoo.com; xuedanshi1991@163.com; wenqianruan@yahoo.com; luojin@gznu.edu.cn; xhwei@pku.edu.cn; 6; 17 |
语种 | 英语 |
内容类型 | 期刊论文 |
源URL | [http://ir.pku.edu.cn/handle/20.500.11897/433261] |
专题 | 化学与分子工程学院 |
推荐引用方式 GB/T 7714 | Li, Lingyun,Hu, Jiwei,Shi, Xuedan,et al. Theoretical Studies on Structures, Properties and Dominant Debromination Pathways for Selected Polybrominated Diphenyl Ethers[J]. INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES,2016. |
APA | Li, Lingyun,Hu, Jiwei,Shi, Xuedan,Ruan, Wenqian,Luo, Jin,&Wei, Xionghui.(2016).Theoretical Studies on Structures, Properties and Dominant Debromination Pathways for Selected Polybrominated Diphenyl Ethers.INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES. |
MLA | Li, Lingyun,et al."Theoretical Studies on Structures, Properties and Dominant Debromination Pathways for Selected Polybrominated Diphenyl Ethers".INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES (2016). |
个性服务 |
查看访问统计 |
相关权益政策 |
暂无数据 |
收藏/分享 |
除非特别说明,本系统中所有内容都受版权保护,并保留所有权利。
修改评论