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It is often suggested that the powerful hydrogen bond between YZ and D1-His190 likely renders YZ kinetically and thermodynamically competent leading to very efficient water oxidation. Nonetheless, an in depth knowledge of the proton-coupled electron transfer (PCET) at YZ stays elusive owing to the transient nature of the intermediate states concerning YZ⋅. Herein, we employ a mix of high-resolution two-dimensional 14N hyperfine sublevel correlation spectroscopy and thickness functional principle