Electron Spin−Lattice Relaxation of the S0 State of the Oxygen-Evolving Complex in Photosystem II and of Dinuclear Manganese Model Complexes

• Published in: Biochemistry (Easton) Vol. 44; no. 26; pp. 9368 - 9374
• Main Authors: Kulik, L. V, Lubitz, W, Messinger, J
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 05.07.2005
• Subjects: Electron Spin Resonance Spectroscopy; Oxygen - chemistry; Photosystem II Protein Complex - chemistry
• ISSN: 0006-2960; 1520-4995
• DOI: 10.1021/bi050411y

The temperature dependence of the electron spin−lattice relaxation time T 1 was measured for the S0 state of the oxygen-evolving complex (OEC) in photosystem II and for two dinuclear manganese model complexes by pulse EPR using the inversion−recovery method. For [Mn(III)Mn(IV)(μ-O)2bipy4]ClO4, the Raman relaxation process dominates at temperatures below 50 K. In contrast, Orbach type relaxation was found for [Mn(II)Mn(III)(μ-OH)(μ-piv)2(Me3tacn)2](ClO4)2 between 4.3 and 9 K. For the latter complex, an energy separation of 24.7−28.0 cm-1 between the ground and the first excited electronic state was determined. In the S0 state of photosystem II, the T 1 relaxation times were measured in the range of 4.3−6.5 K. A comparison with the relaxation data (rate and pre-exponential factor) of the two model complexes and of the S2 state of photosystem II indicates that the Orbach relaxation process is dominant for the S0 state and that its first excited state lies 21.7 ± 0.4 cm-1 above its ground state. The results are discussed with respect to the structure of the OEC in photosystem II.