Primary charge-recombination in an artificial photosynthetic reaction center

Yasuhiro Kobori, Seigo Yamauchi, Kimio Akiyama, Shozo Tero-Kubota, Hiroshi Imahori, Shunichi Fukuzumi, James R. Norris

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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 ≈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,b3g) and 3(au, b3g) electronic states of the free-base porphyrin.

Original languageEnglish
Pages (from-to)10017-10022
Number of pages6
JournalProceedings of the National Academy of Sciences of the United States of America
Issue number29
StatePublished - 19 Jul 2005


  • Electronic coupling
  • Long-range electron transfer
  • Molecular orbital symmetry


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