| Ab initio study of long-range electron transfer between biphenyl anion radical and naphthalene |
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| 作者姓名： | 李象远 肖顺清 何福城 |
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| 作者单位： | Department of Applied Chemistry，Sichuan Union University，Chengdu 610065，China |
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| 基金项目： | Project supported by the National Natural Science Foundation of China (Grant Nos. 29706104 and 29573112)，the State Key Laboratory of Theoretical and Computational Chemistry of Jilin University. |
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| 摘 要： | After the separation of the donor, the aeceptor, and the σ-type bridge from the π-σ-π system, the geometries of biphenyl, biphenyl anion radical, naphthalene, and naphthalene anion radical are optimized, and then the reorganization energy for the intermolecular electron transfer (ET) at the levels of HF/4-31G and HF/DZP is calculated. The ET matrix elements of the self-exchange reactions of the π-σ-π systems have been calculated by means of both the direct calculation based on the variational principle, and the transition energy between the molecular orbitals at the linear coordinate R=0.5. For the cross reactions, the ET matrix element and the geometry of the transition state are determined by searching the minimum energy splitting △_(min) along the reaction coordinate. In the evaluation of the solvent reorganization energy of the ET in solution, the Marcus' two-sphere model has been invoked. A few of ET rate constants for the intramolecular ET reactions for the π-σ-π systems, which contain
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Ab initio study of long-range electron transfer between biphenyl anion radical and naphthalene |
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| LI Xiangyuan XIAO Shunqing HE Fucheng.Ab initio study of long-range electron transfer between biphenyl anion radical and naphthalene[J].Science in China(Chemistry),1999(4). |
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| Authors: | LI Xiangyuan XIAO Shunqing HE Fucheng |
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| Abstract: | |
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| Keywords: | reorganization energy electron transfer matrix element donor and acceptor rate constant |
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