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Theoretical Study on Reactivity of Electron Transfer in Model‐System of Oxidation of α ‐Amino Carbon‐centered Radical by O 2
Author(s) -
Li XiangYuan,
Liu JiFeng,
Yu HuaBin
Publication year - 2002
Publication title -
chinese journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.28
H-Index - 41
eISSN - 1614-7065
pISSN - 1001-604X
DOI - 10.1002/cjoc.20020200907
Subject(s) - chemistry , endothermic process , radical ion , electron transfer , atomic orbital , molecule , ab initio , molecular orbital , ion , reactivity (psychology) , reaction rate constant , computational chemistry , solvent , carbon fibers , electron , organic chemistry , kinetics , medicine , physics , alternative medicine , materials science , adsorption , quantum mechanics , pathology , composite number , composite material
Electron transfer reaction between a simplified model molecule of α‐amino carbon‐centered radical and O 2 has been studied 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 and the reorganization energy. Solvent effects have been considered by applying the conductor‐like screening model. Theoretical results show that the highly endothermic charge separation process, in which one electron transfers from the α‐amino carbon‐centered radical to O 2 , so as to form an ion pair complex, is difficult to occur in gas‐phase. By applying an external electronic field to prepare the charge‐localized molecular orbitals, the charge‐separated state has been obtained 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 O 2 is remarkable. From the rate constant estimation, it can be predicted that the oxidation of the model donor molecule by O 2 can proceed, but not very fast. A peroxyl radical compound has been found to be a competitive intermediate in the oxidation process.