Vibrational analyses of di-μ-oxo-bridged manganese dimers based on density functional theory calculations. Theoretical evaluation of Mn-O vibrations of the Mn-cluster core for photosynthetic oxygen-evolving complex

被引：0

作者：

Hasegawa, Koji ^{[1
,2
]}

Ono, Taka-Aki ^{[1
,3
]}

机构：

[1] Laboratory for Photo-Biology (I), RIKEN Photodynamics Research Center, 519-1399 Aoba, Aramaki, Aoba-ku, Sendai 980-0845

[2] Molecular Membrane Biology Laboratory, RIKEN, 2-1 Hirosawa, Wako 351-0198

[3] Department of Biomolecular Functional Engineering, Faculty of Engineering, Ibaraki University, 4-12-1 Nakanarusawa-cho, Hitachi 316-8511

来源：

Bulletin of the Chemical Society of Japan | 2006年 / 79卷 / 07期

关键词：

Normal coordinate analyses of di-μ-oxo-bridged [Mn2 III; III(μ-O)2(ND3)8; 2+; Mn2III; IV(μ-O)2(ND; 3)8]3+; and; Mn2; IV; IV(μ-O)2(ND3)8]4+ dimers were carried out systematically based on force-constants obtained by B3PW91 hybrid density functional theory (DFT) calculations on a broken-symmetry electronic state. Calculation results indicated that all Mn-O-Mn/Mn-O stretch vibrations are found at 697-387 cm-1 with the strongest infrared (IR) intensities occurring at 620; 697; and 615 cm-1 for Mn 2III; III; and Mn 2IV; IV dimers; respectively; which are compatible with experimental data. These strong IR bands were assigned to the Mn-O-Mn asymmetric stretch 1 (B3u vibration) for the equivalent Mn2 III; III and Mn2IV; IV dimers with D2h symmetry; and the MnIV-O symmetric stretch (A1 vibration) for the mixedvalence Mn2III; IV dimer with C2v symmetry. Based on the results of calculations; the reported 18O-sensitive IR bands in the low-frequency S2/S 1 spectrum in a photosynthetic oxygen-evolving complex (OEC) were assigned to the MnIV-O asymmetric stretch (B2 vibration) in the di-μ-oxo-bridged Mn2III; IV dimer moiety for the S1-state Mn-cluster core and the Mn-O-Mn asymmetric stretch 1 (B 3u vibration) in the di-μ-oxo-bridged Mn2 IV; IV dimer moiety in the S2-state Mn-cluster core. © 2006 The Chemical Society of Japan;

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摘要：

Journal article (JA)

引用

页码：1025 / 1031

共 2 条

[1] Vibrational analyses of di-μ-oxo-bridged manganese dimers based on density functional theory calculations.: Theoretical evaluation of Mn-O vibrations of the Mn-cluster core for photosynthetic oxygen-evolving complex
Hasegawa, Koji
Ono, Taka-aki
[J]. BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 2006, 79 (07) : 1025 - 1031
[2] The Mn cluster in the S0 state of the oxygen-evolving complex of photosystem II studied by EXAFS spectroscopy:: Are there three di-μ-oxo-bridged Mn2 moieties in the tetranuclear Mn complex?
Robblee, JH
Messinger, J
Cinco, RM
McFarlane, KL
Fernandez, C
Pizarro, SA
Sauer, K
Yachandra, VK
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (25) : 7459 - 7471

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