Nicholas Cox 1 , * , Marius Retegan 1 , Frank Neese 1 , Dimitrios A. Pantazis 1 , Alain Boussac 2 , Wolfgang Lubitz 1 , * + Author Affiliations 1 Max Planck Institute for Chemical Energy Conversion, Stiftstrasse 34-36, D-45470 Mülheim an der Ruhr, Germany. 2 Institut de Biologie et de Technologies de Saclay, CNRS UMR 8221, Commissariat à l’Énergie Atomique (CEA) Saclay, 91191 Gif-sur-Yvette, France. ↵ * Corresponding author. E-mail: nicholas.cox@cec.mpg.de (N.C.); wolfgang.lubitz@cec.mpg.de (W.L.) ABSTRACT EDITOR'S SUMMARY The photosynthetic protein complex photosystem II oxidizes water to molecular oxygen at an embedded tetramanganese-calcium cluster. Resolving the geometric and electronic structure of this cluster in its highest metastable catalytic state (designated S 3 ) is a prerequisite for understanding the mechanism of O-O bond formation. Here, multifrequency, multidimensional magnetic resonance spectr...