Reprint of "theory of chemical bonds in metalloenzymes XVIII. Importance of mixed-valence configurations for Mn5O5, CaMn4O5 and Ca2Mn3O5 clusters revealed by UB3LYP computations. A bio-inspired strategy for artificial photosynthesis"

K. Yamaguchi, Y. Kitagawa, Hiroshi Isobe, M. Shoji, S. Yamanaka, M. Okumura

Research output: Contribution to journalArticle

Abstract

Full geometry optimizations of mixed-valence (MV) Mn(II) RMn(II)aMn(IV)b Mn(IV)cMn(III) d (1), Ca(II)RMn(III)aMn(III) bMn(IV)cMn(III)d (2) and Ca(II) RCa(II)a Mn(IV)bMn(IV)cMn(III) d (3) clusters by UB3LYP have been performed to elucidate possible roles of substitutions of Mn(II) with Ca(II) in parent manganese oxides. The optimized Mn-Mn and Mn-Ca distances for 1, 2 and 3 have been compared with the EXAFS and XRD experimental structures of the oxygen evolving complex (OEC) of photosystem II (PSII) to elucidate variations of geometrical structures and valence fluctuations by the substitutions. The optimized Mn-O distances of 1, 2 and 3 have been examined to elucidate Jahn-Teller distortions induced by the Mn(III) ions. The computational results have illuminated possible origins of the elongated Mn-Mn distances and Mn-O distances in the high-resolution XRD structure by Umena et al. Implications of the computational results have been discussed in relation to chemical modifications of multi-nuclear manganese complexes with substitutions of Mn(II) with Ca(II) for rational design of artificial catalysts for water oxidation. A new bio-inspired strategy for artificial photosynthesis is also proposed based on a guiding principle, namely use of hole- and electron-doped strongly correlated electron systems (SCES) for oxidation and reduction reactions instead of conventional semiconductor materials.

Original languageEnglish
Pages (from-to)283-293
Number of pages11
JournalPolyhedron
Volume66
DOIs
Publication statusPublished - 2013

Fingerprint

photosynthesis
Photosynthesis
Chemical bonds
chemical bonds
Substitution reactions
valence
substitutes
configurations
Jahn-Teller effect
Oxidation
Photosystem II Protein Complex
Manganese oxide
Electrons
Chemical modification
Manganese
oxidation
manganese oxides
Ions
Semiconductor materials
Oxygen

Keywords

  • Artificial photosynthesis
  • CaMnO
  • Geometry optimization
  • Mixed valence
  • Strongly correlation electron systems (SCES)
  • UB3LYP
  • Water oxidation

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Materials Chemistry
  • Physical and Theoretical Chemistry

Cite this

@article{2c2ddec399484a1ca993ef1864d8b707,
title = "Reprint of {"}theory of chemical bonds in metalloenzymes XVIII. Importance of mixed-valence configurations for Mn5O5, CaMn4O5 and Ca2Mn3O5 clusters revealed by UB3LYP computations. A bio-inspired strategy for artificial photosynthesis{"}",
abstract = "Full geometry optimizations of mixed-valence (MV) Mn(II) RMn(II)aMn(IV)b Mn(IV)cMn(III) d (1), Ca(II)RMn(III)aMn(III) bMn(IV)cMn(III)d (2) and Ca(II) RCa(II)a Mn(IV)bMn(IV)cMn(III) d (3) clusters by UB3LYP have been performed to elucidate possible roles of substitutions of Mn(II) with Ca(II) in parent manganese oxides. The optimized Mn-Mn and Mn-Ca distances for 1, 2 and 3 have been compared with the EXAFS and XRD experimental structures of the oxygen evolving complex (OEC) of photosystem II (PSII) to elucidate variations of geometrical structures and valence fluctuations by the substitutions. The optimized Mn-O distances of 1, 2 and 3 have been examined to elucidate Jahn-Teller distortions induced by the Mn(III) ions. The computational results have illuminated possible origins of the elongated Mn-Mn distances and Mn-O distances in the high-resolution XRD structure by Umena et al. Implications of the computational results have been discussed in relation to chemical modifications of multi-nuclear manganese complexes with substitutions of Mn(II) with Ca(II) for rational design of artificial catalysts for water oxidation. A new bio-inspired strategy for artificial photosynthesis is also proposed based on a guiding principle, namely use of hole- and electron-doped strongly correlated electron systems (SCES) for oxidation and reduction reactions instead of conventional semiconductor materials.",
keywords = "Artificial photosynthesis, CaMnO, Geometry optimization, Mixed valence, Strongly correlation electron systems (SCES), UB3LYP, Water oxidation",
author = "K. Yamaguchi and Y. Kitagawa and Hiroshi Isobe and M. Shoji and S. Yamanaka and M. Okumura",
year = "2013",
doi = "10.1016/j.poly.2013.08.003",
language = "English",
volume = "66",
pages = "283--293",
journal = "Polyhedron",
issn = "0277-5387",
publisher = "Elsevier Limited",

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TY - JOUR

T1 - Reprint of "theory of chemical bonds in metalloenzymes XVIII. Importance of mixed-valence configurations for Mn5O5, CaMn4O5 and Ca2Mn3O5 clusters revealed by UB3LYP computations. A bio-inspired strategy for artificial photosynthesis"

AU - Yamaguchi, K.

AU - Kitagawa, Y.

AU - Isobe, Hiroshi

AU - Shoji, M.

AU - Yamanaka, S.

AU - Okumura, M.

PY - 2013

Y1 - 2013

N2 - Full geometry optimizations of mixed-valence (MV) Mn(II) RMn(II)aMn(IV)b Mn(IV)cMn(III) d (1), Ca(II)RMn(III)aMn(III) bMn(IV)cMn(III)d (2) and Ca(II) RCa(II)a Mn(IV)bMn(IV)cMn(III) d (3) clusters by UB3LYP have been performed to elucidate possible roles of substitutions of Mn(II) with Ca(II) in parent manganese oxides. The optimized Mn-Mn and Mn-Ca distances for 1, 2 and 3 have been compared with the EXAFS and XRD experimental structures of the oxygen evolving complex (OEC) of photosystem II (PSII) to elucidate variations of geometrical structures and valence fluctuations by the substitutions. The optimized Mn-O distances of 1, 2 and 3 have been examined to elucidate Jahn-Teller distortions induced by the Mn(III) ions. The computational results have illuminated possible origins of the elongated Mn-Mn distances and Mn-O distances in the high-resolution XRD structure by Umena et al. Implications of the computational results have been discussed in relation to chemical modifications of multi-nuclear manganese complexes with substitutions of Mn(II) with Ca(II) for rational design of artificial catalysts for water oxidation. A new bio-inspired strategy for artificial photosynthesis is also proposed based on a guiding principle, namely use of hole- and electron-doped strongly correlated electron systems (SCES) for oxidation and reduction reactions instead of conventional semiconductor materials.

AB - Full geometry optimizations of mixed-valence (MV) Mn(II) RMn(II)aMn(IV)b Mn(IV)cMn(III) d (1), Ca(II)RMn(III)aMn(III) bMn(IV)cMn(III)d (2) and Ca(II) RCa(II)a Mn(IV)bMn(IV)cMn(III) d (3) clusters by UB3LYP have been performed to elucidate possible roles of substitutions of Mn(II) with Ca(II) in parent manganese oxides. The optimized Mn-Mn and Mn-Ca distances for 1, 2 and 3 have been compared with the EXAFS and XRD experimental structures of the oxygen evolving complex (OEC) of photosystem II (PSII) to elucidate variations of geometrical structures and valence fluctuations by the substitutions. The optimized Mn-O distances of 1, 2 and 3 have been examined to elucidate Jahn-Teller distortions induced by the Mn(III) ions. The computational results have illuminated possible origins of the elongated Mn-Mn distances and Mn-O distances in the high-resolution XRD structure by Umena et al. Implications of the computational results have been discussed in relation to chemical modifications of multi-nuclear manganese complexes with substitutions of Mn(II) with Ca(II) for rational design of artificial catalysts for water oxidation. A new bio-inspired strategy for artificial photosynthesis is also proposed based on a guiding principle, namely use of hole- and electron-doped strongly correlated electron systems (SCES) for oxidation and reduction reactions instead of conventional semiconductor materials.

KW - Artificial photosynthesis

KW - CaMnO

KW - Geometry optimization

KW - Mixed valence

KW - Strongly correlation electron systems (SCES)

KW - UB3LYP

KW - Water oxidation

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U2 - 10.1016/j.poly.2013.08.003

DO - 10.1016/j.poly.2013.08.003

M3 - Article

VL - 66

SP - 283

EP - 293

JO - Polyhedron

JF - Polyhedron

SN - 0277-5387

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