Theoretical Study on Reactivity of Electron Transfer in Model-System of Oxidation of α-Amino Carbon-centered Radical by O2

• 来源期刊: 中国化学（英文版）
• 年，卷（期）: 2002,（9）
• 页码范围: 834-840
• 页数: 7页
• 语种: 英文

摘要

Electrontransfer reaction between a simplified model molecule ofα-amino carbon-centered radical and O2 has beentudied with ab initio calculations at the MP2/6-31 ++ G**//UHF/6-31++G**level.The reactant complex and the ion pair complex have been optimized and employed to perform calculations of the reaction heat andthe reorganization energy.Solvent effects have been considered by applying he conductor-like screening model.Theoretical results show that the highly endothermic charge separation process,in which one electron transfersfrom theα-amino carbon-centered radical to O2,so as to form an ion pari complex,is difficult to occur in gas-phase.By applying an external electronic field to prepar the charge-localized molecular orbitals,the charge-separated state has been obtain using the initial-guess-induced self-consistent field technique.The theoretical investigations indicate that the solvent effect in the process of the oxidation of α-amino carbon-centered radical by O2 is remarkable.From the rate constant estimation ,it can be predicted thatthe oxidation of the model donor molecule by O2 can proceed,but not veryfast.A peroxyl radical compound has been found to be a competitive intermediate in the oxidation proces.