Seminar: Novel electrolytes for electrochemical energy storage devices: from identification to application

May 24^th 2023, Sala Riunioni at 11:30 am

Mechanistic investigations of the water-splitting reaction of the oxygen-evolving complex (OEC) of photosystem II (PSII) are fundamentally informed by structural studies of oxomanganese complexes. Many physical techniques have provided important insights into the OEC structure and function, including X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) spectroscopy as well as mass spectrometry (MS), electron paramagnetic resonance (EPR) spectroscopy, and Fourier transform infrared spectroscopy applied in conjunction with mutagenesis studies. However, experimental studies have yet to yield consensus as to the nature of the reaction mechanism responsible for oxygen evolution. In this lecture, computational modeling studies will be introduced, including density functional (DFT) theory combined with quantum mechanics/molecular mechanics (QM/MM) hybrid methods for explicitly describing the influence of the surrounding protein proposed chemically satisfactory models of the OEC that are maximally consistent with experimental results. The computational models are useful for rationalizing spectroscopic and crystallographic results and for building a complete structure-based mechanism of water-splitting as described by the intermediate oxidation states of oxomanganese complexes. Recent advances will be reviewed with emphasis on studies of the OEC of PSII and semiconductor materials functionalized biomimetic catalysts for artificial photosynthesis.