| NH_3/NH_3~+体系电子转移性的黄金规则研究 |
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| 引用本文： | 孙巧,步宇翔.NH_3/NH_3~+体系电子转移性的黄金规则研究[J].化学学报,2002,60(3):413-418. |
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| 作者姓名： | 孙巧 步宇翔 |
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| 作者单位： | 1. 曲阜师范大学化学系,曲阜,273165
2. 曲阜师范大学化学系,曲阜,273165山东大学理论化学研究所,济南,250100 |
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| 基金项目： | 国家自然科学基金 (No .2 99730 2 2 )，教育部骨干教师计划项目资助课题 |
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| 摘 要： | 用密度泛函理论(BEP86, B3LYP)在6-31G~*, 6-311+G~*基组水平上和从头算方 法MP2(FULL)/6-311+G~*]优化了NH_3和NH_3~+以及复合物(NH_3…NH_3)~*的几何 构型，计算了体系稳定化能，然后用MP2（FULL）／6－311＋G”＊方法扫描势有面 找出不同N－N接触距离的活化志体系的能量、活化能、耦合矩阵元，利用黄金规则 计算出不同的N－N接触距离的电子转移速率。并讨论了活化态体系的能量、活化能 、耦合矩辄元和Franck-Condon因子及电子转移速率与接触距离的依赖关系。进一 步验证了黄金规则应用于电子转移反应的正确性。
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| 关 键 词： | 氨 从头计算法 耦合 电子转移反应 |
| 修稿时间： | 2001年6月28日 |
Golden-rule Study of Electron Transfer Reactivity of NH_3/NH_3~+ System |
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| SUN,Qiao a BU,Yu-Xiang,a,b.Golden-rule Study of Electron Transfer Reactivity of NH_3/NH_3~+ System[J].Acta Chimica Sinica,2002,60(3):413-418. |
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| Authors: | SUN Qiao a BU Yu-Xiang a b |
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| Institution: | Department of Chemistry, Qufu Normal University,Qufu(273165) |
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| Abstract: | Density function theory (B3P86, B3LYP) at 6-31G * and 6-311+G * basis set levels and ab initio calculation at 6-311+G * basis set level are used to optimize the molecular structures of NH 3, NH 3 + and the complex (NH 3...NH 3) +. The stabilization energy of this system is calculated. Then at 6-311+G * basis set level MP2(FULL) method is used to scan the potential energy surface of different N-N contact distance in order to obtain the energies, activation energies, coupling matrix elements and Franck-Condon factors of this system. The electron transfer rate is calculated by using the Golden-rule scheme. Finally, the contact distance dependence of these kinetics quantities is discussed. The rationality of Golden-rule has been justified for the application to ET system once again. |
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| Keywords: | NH 3/NH 3 + system density function theory ab initio golden-rule coupling matrix element electron-transfer rate |
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