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利用ab initio方法,在UHF,UMP2及不同基组3-21G,6-31G~*,6-311+G~*和UMP2(full)/6-311+G~*水平上,研究了O_2/O_2~-自交换电子转移反应.优化了电子转移前后反应物和产物的结构,研究了体系能量的变化,计算了自交换电子转移反应的内重组能.对UHF方法和UMP2方法的计算结果进行了比较,并与实验结果进行了对照.结果表明UHF方法由于没有考虑组态相互作用,计算结果存在较大偏差,UMP2(full)/6-311+G~*水平上的计算结果与实验值吻合较好.在UMP2(full)/6-311+G~*水平上计算了气相自交换电子转移反应速率常数.在优化了电子转移复合物结构的基础上考虑了溶剂效应的影响,计算了水溶液中的溶剂重组能.研究结果表明O_2/O_2~-体系电子转移反应的活化能主要来源于溶剂重组能的贡献.最后计算了该反应在水溶液中的反应速率常数.理论计算结果与实验值吻合得很好.
The ab initio method was used to study the effect of O_2 / O_2 on the levels of 3-21G, 6-31G ~ *, 6-311 + G ~ * and UMP2 (full) / 6-311 + G ~ * in UHF, O_2 ~ - self-exchange electron transfer reaction.The structures of the reactants and products before and after the electron transfer were optimized, the energy change of the system was studied, and the internal reorganization energy of the self-exchange electron transfer reaction was calculated.The calculation results of UHF method and UMP2 method were calculated The results show that the UHF method does not consider the configuration interaction, and the calculated results have large deviations. The calculated results of UMP2 (full) / 6-311 + G ~ * are in good agreement with the experimental values Good agreement was obtained.The rate constants of gas-phase electron exchange reaction were calculated at the level of UMP2 (full) / 6-311 + G ~ * and the effect of solvent effect was considered on the basis of optimizing the structure of electron transfer complex The results show that the activation energy of the electron transfer reaction of O 2 / O 2 ~ - system mainly comes from the contribution of solvent recombination energy. Finally, the reaction rate constant of the reaction in aqueous solution is calculated. The calculated results are in good agreement with the experimental data Good agreement.