Uncovering quantum characteristics of incipient evolutions at the photosynthetic oxygen evolving complex

Abstract

Water oxidation of photosynthesis at the oxygen evolving complex (OEC) is driven by the polarization field induced by the photoelectric hole. By highlighting the role of the polarization field in reshaping the spin and orbit potentials, we reveal in this work the characteristics and underlying mechanism in the relatively simpler OEC evolutions within the states S0–S2 prior to the water oxidation. The characteristic shifts of the density of states (DOS) of the electron donor Mn atom are observed in the vicinity of the Fermi surface to occur with the spin flips of Mn atoms and the change in the Mn oxidation states during the electron transfer. Notably, the spin flips of Mn atoms point to the resulting spin configuration of the next states. It is found that the electron transfer tends to stabilize the catalyst OEC itself, whereas the proton transfer pushes the evolution forward by preparing a new electron donor, demonstrating the proton-coupled electron transfer. Meanwhile, it shows that the Mn–O bonds around the candidate Mn atom of the electron donor undergo characteristic changes in the bond lengths during the electron transfer. These concomitant phenomena uncovered in first-principle calculations characterize the essential equilibrium of the OEC between the state evolution and stability that forms the groundwork of the dynamic OEC cycles. In particular, the characteristic undulation of the DOS around the Fermi level occurring at the proton-coupled electron transfer can be used to reveal crucial processes in a wide range of realistic systems.