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

doi:10.1073/pnas.0504598102

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

Department of Chemistry & Nanoscience

Research output: Contribution to journal › Article › peer-review

80 Scopus citations

Abstract

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,b_3g) and ³(a_u, b_3g) electronic states of the free-base porphyrin.

Original language	English
Pages (from-to)	10017-10022
Number of pages	6
Journal	Proceedings of the National Academy of Sciences of the United States of America
Volume	102
Issue number	29
DOIs	https://doi.org/10.1073/pnas.0504598102
State	Published - 19 Jul 2005

Keywords

Electronic coupling
Long-range electron transfer
Molecular orbital symmetry

Access to Document

10.1073/pnas.0504598102

Cite this

@article{a7c8beedc4524de4b28f0408c233197f,

title = "Primary charge-recombination in an artificial photosynthetic reaction center",

abstract = "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.",

keywords = "Electronic coupling, Long-range electron transfer, Molecular orbital symmetry",

author = "Yasuhiro Kobori and Seigo Yamauchi and Kimio Akiyama and Shozo Tero-Kubota and Hiroshi Imahori and Shunichi Fukuzumi and Norris, {James R.}",

year = "2005",

month = jul,

day = "19",

doi = "10.1073/pnas.0504598102",

language = "English",

volume = "102",

pages = "10017--10022",

journal = "Proceedings of the National Academy of Sciences of the United States of America",

issn = "0027-8424",

publisher = "National Academy of Sciences",

number = "29",

}

TY - JOUR

T1 - Primary charge-recombination in an artificial photosynthetic reaction center

AU - Kobori, Yasuhiro

AU - Yamauchi, Seigo

AU - Akiyama, Kimio

AU - Tero-Kubota, Shozo

AU - Imahori, Hiroshi

AU - Fukuzumi, Shunichi

AU - Norris, James R.

PY - 2005/7/19

Y1 - 2005/7/19

N2 - 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.

AB - 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.

KW - Electronic coupling

KW - Long-range electron transfer

KW - Molecular orbital symmetry

UR - http://www.scopus.com/inward/record.url?scp=22544438110&partnerID=8YFLogxK

U2 - 10.1073/pnas.0504598102

DO - 10.1073/pnas.0504598102

M3 - Article

C2 - 16014413

AN - SCOPUS:22544438110

SN - 0027-8424

VL - 102

SP - 10017

EP - 10022

JO - Proceedings of the National Academy of Sciences of the United States of America

JF - Proceedings of the National Academy of Sciences of the United States of America

IS - 29

ER -

Primary charge-recombination in an artificial photosynthetic reaction center

Abstract

Keywords

Access to Document

Fingerprint

Cite this