Primary charge-recombination in an artificial photosynthetic reaction center
Primary charge-recombination in an artificial photosynthetic reaction center
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DOI：
10.1073/pnas.0504598102
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发表时间：
2005-07-19
影响因子：
11.1
通讯作者：
Norris, JR
中科院分区：
文献类型：
--
作者：
Kobori, Y;Yamauchi, S;Norris, JR
光致初级电荷分离和电荷复合是通过时间分辨光学测量和EPR测量相结合的富勒烯-卟啉连接的三元化合物经历快速、逐步的电荷分离过程来表征的。从短寿命初级电荷分离态的单态-三态电子能隙来评价耗能电荷复合的电子耦合。电子耦合比一次电荷分离的电子耦合小约40%。这种电荷复合到激发三重态的电子相互作用的抑制很大程度上是由于自由基卟啉的(3)(b(1u)，b(3g))电子态和(3)(a(U)，b(3g))电子态之间的组态相互作用调制的对称性破缺电子结构。
Photoinduced primary charge-separation and charge-recombination are characterized by a combination of time-resolved optical and EPR measurements of a fullerene-porphyrin-linked triad that undergoes fast, stepwise charge-separation processes. The electronic coupling for the energy-wasting charge recombination is evaluated from the singlet-triplet electronic energy gap in the short-lived, primary charge-separated state. The electronic coupling is found to be smaller by approximate to 40% than that for the primary charge-separation. This inhibition of the electronic interaction for the charge-recombination to excited triplet state largely results from a symmetry-broken electronic structure modulated by configuration interaction between (3)(b(1u),b(3g)) and (3)(a(u), b(3g)) electronic states of the free-base porphyrin.