气相中Fe2+和H2O2作用生成OH自由基的理论研究

利用B3LYP方法，在6-311G基组下研究了气相中Fe~(2+)与H_2O_2作用生成OH自 由基的反应途径，探讨了铁离子对生成羟基自由基所起的作用。结果表明反应的途 径为：Fe~(2+)与H_2O_2首先形成中间体（FeO_2H_2）~(2+)，然后能过O-O键的断 裂生成中间体（HOFeOH）~(2+)，再断Fe-OH键生成羟基自由基，Fe~(2+)和H_2O_2 的电荷强烈相互作用以及Fe~(2+)的d轨道上的电子促进H_2O_2中的O-O键断裂，生 成羟基自由基。

Theoretical Study on OH Radical Generation from the Reaction of Fe~ (2+) and H_2O_2 in Gas Phase

The reaction pathway in which OH radical generated from ihe interaction of Fe~(2+) with H_2O_2 was investigated theoretically at the B3LYP/6-311G* * level. The role of ferrous ion in the radical generation was studied. The most favarable reaction pathway was confirmed. Interaction of Fe with H_2O_2 produces an intermediate complex (FeO_2H_2)~(2+) . Then 0-0 bond breaks to produce an intermediate complex (HOFeOH)~(2+) . Fe-OH bond breaks to produce OH radical. In the reaction, the strong charge interaction of Fe~(2+) with H_2O_2 ami the d orbital electron of Fe~(2+) promote the cleavage of 0-0 bond. The existence of ferrous favors the generation of OH radical.