摘要
The mechanism of the multiple-pathway and multiple-step degradation reactions of 2,3,7,8-tetrachlorinated dibenzo-p-dioxins with H and Cl atoms is investigated using the density functional theory.The electronic structures and the minimum energy path(MEP)are calculated at the B3LYP/6-311+G(d,p)level,and energetic information(single-point)is further refined at the B3LYP/6-311++G(3df,2p)level.The main possible ring opening reaction pathways of the C–O bond breakdown include indirect cleavage ring opening reaction,hydrogen addition reaction,hydrogen addition elimination reaction,and chlorine addition elimination reaction.Ten reaction steps of the six reaction pathways are considered.Our calculations indicate that hydrogen addition reaction step TS1c is of the smallest barrier height,and indirect cleavage ring opening reaction channel has the largest barrier height and is the most endothermic.
基金
supported by the Innovative Research Team of Green Chemical Technology in University of Heilongjiang Province.
supported by the National Basic Research Program of China("973"Project)(Grant No.2012CB723308)
the National Natural Science Foundation of China(Grant Nos.51337002 and 50977019)
the Doctoral Foundation by the Ministry of Education of China(Grant No.20112303110005)
the Science Foundation for Distinguished Young Scholar of Heilongjiang Province(Grant No.JC201206)
