Block-Localized Wavefunction (BLW) Based Two-State Approach for Charge Transfers between Phenyl Rings

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• 作者：Yirong Mo ; Lingchun Song ; Yuchun Lin ; Minghong Liu ; Zexing Cao ; Wei Wu
• 刊名：Journal of Chemical Theory and Computation
• 出版年：2012
• 出版时间：March 13, 2012
• 年：2012
• 卷：8
• 期：3
• 页码：800-805
• 全文大小：327K
• 年卷期：v.8,no.3(March 13, 2012)
• ISSN：1549-9626

文摘

The block-localized wave function (BLW) method is the simplest and most efficient variant of ab initio valence bond (VB) theory which defines electron-localized resonance states following the conventional VB concepts. Here, a BLW-based two-state approach is proposed to probe the charge/hole transfer reactions within the Marcus鈥揌ush model. With this approach, both the electronic coupling and reorganization energies can be derived at the ab initio level. Pilot applications to the electron/hole transfers between two phenyl rings are presented. Good exponential correlation between the electronic coupling energy and the donor鈥揳cceptor distance is shown, whereas the inner-sphere reorganization shows little geometric dependency. Computations also support the assumption in Marcus theory that the thermal electron transfer barrier (螖G*), which is a sum of the reaction barrier (螖E_a) for electron/hole transfer and the coupling energy (V_AB), is a quarter of the reorganization energy (位).