Computational studies of the Mn4/Ca cluster in photosystem II

Abstract

Computational chemistry with the data from more detailed X-ray diffraction (XRD) oxygen evolving complex (OEC) structure has been used extensively of late in exploring the mechanisms of water oxidation in the OEC. The study reported in this paper involves density functional theory (DFT) calculations to investigate whether the data are in agreement with the four manganese ions in the OEC, being organized as a ‘3[Formula: see text]1’ (trimer plus one) model [Gatt et al. Angewandte Chemie International Edition, 51, 12025–12028, 2012; Petrie et al. Chemistry - A European Journal, 21, 6780–6792, 2015; Terrett et al. Chemical Communications, 50, 3187–3190, 2014] or ‘dimer of dimers’ model. [Terrett et al. Journal of Inorganic Biochemistry, 162, 178–189, 2016]. The data analysis method used involves quantum chemical DFT calculations on relevant models of the OEC cluster. DFT calculations were performed using both the so-called ‘open’ and ‘closed’ forms [Terrett et al. Journal of Inorganic Biochemistry, 162, 178–189, 2016] of the S2 OEC structure models with total spin ([Formula: see text]) 1/2, 7/2, 9/2 and 15/2 within the MnIII MnIV MnIII MnIII ‘low’ oxidation paradigm to examine exchange coupling within the OEC cluster. The results show that the [Formula: see text]-coupling in the ‘closed’ form: [Formula: see text][Formula: see text]cm[Formula: see text], [Formula: see text][Formula: see text]cm[Formula: see text], [Formula: see text][Formula: see text]cm[Formula: see text] and [Formula: see text]–[Formula: see text][Formula: see text]cm[Formula: see text]. In the ‘closed’ form, [Formula: see text] and [Formula: see text] represent the two largest exchange interactions within the manganese cluster, whereas [Formula: see text] and [Formula: see text] are small and almost net cancel. The magnetic coupling between the four Mn ions is close to ‘dimer of dimers’, with both dimers anti-ferromagnetically coupled internally and with weak inter-dimer net coupling.