| Theoretical Study on Electron Transfer Matrix Element in Oxidation of α—Amino Carbon—Centered Radical by O2 |
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| 引用本文： | 刘继凤,朱权,李象远,杨胜勇.Theoretical Study on Electron Transfer Matrix Element in Oxidation of α—Amino Carbon—Centered Radical by O2[J].中国化学,2002,20(10):972-977. |
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| 作者姓名： | 刘继凤 朱权 李象远 杨胜勇 |
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| 作者单位： | CollegeofChemicalEngineering,SichuanUniversity,chengdu,Sichuan610065,china |
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| 基金项目： | ProjectsupportedbytheNationalNaturalScienceFoundationofChina (Nos.2 9892 16 4and 39970 183) |
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| 摘 要： | As a successive work of our previous paper,^1the electron transfer matrix element(Vrp)in the oxidation of the simplified model molecule of α-amino carbon-centered radical by O2 has been investigated with ab initio calculation at the level of UHF/6-31 G**.Based on the optimized geometries of the reactgant and the ion-pair complex obtained previously,the reaction heat and the iuner reorganization energy have been obtained by constructing the potential energy curves of reactant and product states considering the solvent effect with the conductor-like screening model(COSMO).The solvent reorganization energy has been estimated using Lippert-Mataga relationship.The calculated results show that the value of Vrp is several times larger than that of RT,which means that the model reaction is an adiabatic one.Theoretical investigation indicates that the solvent effect on the direct electron transfer (ET) process of oxidation of α-amino carbon-centered radical by oxygen is remarkable.
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| 关 键 词： | 溶解能 电子转移 理论研究 基体元素 氧化物 反应机理 |
Theoretical Study on Electron Transfer Matrix Element in Oxidation of α ‐ Amino Carbon‐Centered Radical by O2 |
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| LIU,Ji-Feng ZHU,Quan LI,Xiang-Yuan YANG,Sheng-YongCollege of Chemical Engineering,Sichuan University,Chengdu,Sichuan ,China.Theoretical Study on Electron Transfer Matrix Element in Oxidation of α ‐ Amino Carbon‐Centered Radical by O2[J].Chinese Journal of Chemistry,2002,20(10):972-977. |
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| Authors: | LIU Ji-Feng ZHU Quan LI Xiang-Yuan YANG Sheng-YongCollege of Chemical Engineering Sichuan University Chengdu Sichuan China |
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| Institution: | LIU,Ji-Feng ZHU,Quan LI,Xiang-Yuan YANG,Sheng-YongCollege of Chemical Engineering,Sichuan University,Chengdu,Sichuan 610065,China |
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| Abstract: | As a successive work of our previous paper,1 the electron transfer matrix element (Vrp) in the oxidation of the simplified model molecule of α‐amino carbon‐centered radical by O2 has been investigated with ab initio calculation at the level of UHF/6‐31 + + G*. Based on the optimized geometries of the reactant and the ion‐pair complex obtained previously, the reaction heat and the inner reorganization energy have been obtained by constructing the potential energy curves of reactant and product states considering the solvent effect with the conductor‐like screening model (COSMO). The solvent reorganization energy has been estimated using Lippert‐Mataga relationship. The calculated results show that the value of Vrp, is several times larger than that of RT, which means that the model reaction is an adiabatic one. Theoretical investigation indicates that the solvent effect on the direct electron transfer (ET) process of oxidation of α‐amino carbon‐centered radical by oxygen is remarkable. |
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| Keywords: | electron transfer solvent reorganization energy ET matrix element |
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