Abstract
Electronic and spin states of putative ruthenium (Ru)-quinine(Q) complex(1) mononuclear[Ru(trpy)(3,5-t-Bu 2Q)(OH 2)(trpy = 2,2':6',2′-terpyridine, 3,5-di-tert-butyl-1,2-benzoquinone)(2) and binuclear [Ru 2(btpyan)(3,6-di-Bu 2Q) 2(OH 2)](SbF 6) 2 (btpyan = 1,8-bis(2,2':6',2′- terpyrid-4'-yl)anthracene,3,6-t-Bu 2Q = 3,6-di-tert-butyl-1,2- benzoquinone) (3) were investigated by broken-symmetry (BS) hybrid density functional (DFT) methods. BS DFT computations for 3 have elucidated that the closed-shell structure (3b): Ru(II)-quinone (Q) complex is less stable than the open-shell structure (3bb) consisted of Ru(III) and semiquinone fragments. These computations have also elucidated eight different electronic and spin structures of tetraradical intermediates generated in the course of water splitting reaction. The Heisenberg spin Hamiltonian model has been derived to elucidate common theoretical pictures for these systems. Effective exchange interactions for four spin systems have been determined using total energies of the 15 different DFT functionals. The natural orbital (NO) analysis of these BS DFT solutions have also been performed to elucidate the NOs and their occupation numbers that are useful for lucid understanding of the nature of chemical bonds of these Ru complexes (1, 2, and 3). Implications of the computational results are discussed in relation to proposed reaction mechanisms of water splitting reaction in artificial photosynthesis systems, similarity between artificial and native water splitting systems, and elements science of water splitting reaction.
| Original language | English |
|---|---|
| Pages (from-to) | 3849-3866 |
| Number of pages | 18 |
| Journal | International Journal of Quantum Chemistry |
| Volume | 112 |
| Issue number | 24 |
| DOIs | |
| Publication status | Published - Dec 15 2012 |
| Externally published | Yes |
Fingerprint
Keywords
- artificial and native models
- radical Intermediates
- ruthenium complexes
- spin Hamiltonian
- water splitting reaction
ASJC Scopus subject areas
- Condensed Matter Physics
- Atomic and Molecular Physics, and Optics
- Physical and Theoretical Chemistry
Cite this
Spin hamiltonian models for artificial and native water splitting systems revealed by hybrid DFT calculations. Oxygen activation by high-valent Mn and Ru ions. / Yamaguchi, K.; Yamanaka, S.; Isobe, Hiroshi; Tanaka, K.; Ueyama, N.
In: International Journal of Quantum Chemistry, Vol. 112, No. 24, 15.12.2012, p. 3849-3866.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Spin hamiltonian models for artificial and native water splitting systems revealed by hybrid DFT calculations. Oxygen activation by high-valent Mn and Ru ions
AU - Yamaguchi, K.
AU - Yamanaka, S.
AU - Isobe, Hiroshi
AU - Tanaka, K.
AU - Ueyama, N.
PY - 2012/12/15
Y1 - 2012/12/15
N2 - Electronic and spin states of putative ruthenium (Ru)-quinine(Q) complex(1) mononuclear[Ru(trpy)(3,5-t-Bu 2Q)(OH 2)(trpy = 2,2':6',2′-terpyridine, 3,5-di-tert-butyl-1,2-benzoquinone)(2) and binuclear [Ru 2(btpyan)(3,6-di-Bu 2Q) 2(OH 2)](SbF 6) 2 (btpyan = 1,8-bis(2,2':6',2′- terpyrid-4'-yl)anthracene,3,6-t-Bu 2Q = 3,6-di-tert-butyl-1,2- benzoquinone) (3) were investigated by broken-symmetry (BS) hybrid density functional (DFT) methods. BS DFT computations for 3 have elucidated that the closed-shell structure (3b): Ru(II)-quinone (Q) complex is less stable than the open-shell structure (3bb) consisted of Ru(III) and semiquinone fragments. These computations have also elucidated eight different electronic and spin structures of tetraradical intermediates generated in the course of water splitting reaction. The Heisenberg spin Hamiltonian model has been derived to elucidate common theoretical pictures for these systems. Effective exchange interactions for four spin systems have been determined using total energies of the 15 different DFT functionals. The natural orbital (NO) analysis of these BS DFT solutions have also been performed to elucidate the NOs and their occupation numbers that are useful for lucid understanding of the nature of chemical bonds of these Ru complexes (1, 2, and 3). Implications of the computational results are discussed in relation to proposed reaction mechanisms of water splitting reaction in artificial photosynthesis systems, similarity between artificial and native water splitting systems, and elements science of water splitting reaction.
AB - Electronic and spin states of putative ruthenium (Ru)-quinine(Q) complex(1) mononuclear[Ru(trpy)(3,5-t-Bu 2Q)(OH 2)(trpy = 2,2':6',2′-terpyridine, 3,5-di-tert-butyl-1,2-benzoquinone)(2) and binuclear [Ru 2(btpyan)(3,6-di-Bu 2Q) 2(OH 2)](SbF 6) 2 (btpyan = 1,8-bis(2,2':6',2′- terpyrid-4'-yl)anthracene,3,6-t-Bu 2Q = 3,6-di-tert-butyl-1,2- benzoquinone) (3) were investigated by broken-symmetry (BS) hybrid density functional (DFT) methods. BS DFT computations for 3 have elucidated that the closed-shell structure (3b): Ru(II)-quinone (Q) complex is less stable than the open-shell structure (3bb) consisted of Ru(III) and semiquinone fragments. These computations have also elucidated eight different electronic and spin structures of tetraradical intermediates generated in the course of water splitting reaction. The Heisenberg spin Hamiltonian model has been derived to elucidate common theoretical pictures for these systems. Effective exchange interactions for four spin systems have been determined using total energies of the 15 different DFT functionals. The natural orbital (NO) analysis of these BS DFT solutions have also been performed to elucidate the NOs and their occupation numbers that are useful for lucid understanding of the nature of chemical bonds of these Ru complexes (1, 2, and 3). Implications of the computational results are discussed in relation to proposed reaction mechanisms of water splitting reaction in artificial photosynthesis systems, similarity between artificial and native water splitting systems, and elements science of water splitting reaction.
KW - artificial and native models
KW - radical Intermediates
KW - ruthenium complexes
KW - spin Hamiltonian
KW - water splitting reaction
UR - http://www.scopus.com/inward/record.url?scp=84869080397&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84869080397&partnerID=8YFLogxK
U2 - 10.1002/qua.24270
DO - 10.1002/qua.24270
M3 - Article
VL - 112
SP - 3849
EP - 3866
JO - International Journal of Quantum Chemistry
JF - International Journal of Quantum Chemistry
SN - 0020-7608
IS - 24
ER -