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用密度泛函理论分别研究气相和水相中的6种氯代酚(2-CP,3-CP,4-CP,2,4-DCP,2,4,6-TCP和PCP)与单线态氧的反应机理。在B3LYP/6-31+G(d,p)水平上,将可能路径上的反应复合物、过渡态和产物分别全优化几何结构和计算频率,通过内禀反应坐标(IRC)的方法验证反应路径,并在B3LYP/6-311+(2df,p)水平上计算单点能。采用极化统一模型(PCM)法探索溶剂效应。结果,不论气相还是水相,1,3加成生成1个烯丙基氢过氧化物和1,4加成生成1个酮类氢过氧化物,在热力学上均是可行的,但是在动力学上前者的能垒比后者更低,是优先路径。热力学更支持在水相中反应,而动力学则相反。能垒随氯代数量的增多而升高。
Density functional theory (DFT) was used to study the interaction between the 6 chlorophenols (2-CP, 3-CP, 4-CP, 2,4-DCP, 2,4,6-TCP and PCP) Oxygen reaction mechanism. At the B3LYP / 6-31 + G (d, p) level, the geometries and frequencies of the reaction complexes, transition states and products on the possible paths were optimized respectively and the reaction was verified by the intrinsic reaction coordinate (IRC) Path and calculate the single point energy at the B3LYP / 6-311 + (2df, p) level. Solvent effects were explored using the Polarization Uniform Model (PCM) method. As a result, it is thermodynamically feasible to generate 1,3-allyl hydroperoxide in 1,3-addition and 1,4-addition to 1-ketohydroperoxide, both in gas phase and in aqueous phase. However, The former has a lower energy barrier than the latter and is the priority. Thermodynamics more support the reaction in the aqueous phase, while the kinetics are the opposite. Energy barrier with the increase in the number of chlorinated and increased.