caa a22 4500 605546215 CHVBK 20210128100939.0 cr unu---uuuuu 210128e20150201xx s 000 0 eng 10.1007/s00723-014-0627-2 doi (NATIONALLICENCE)springer-10.1007/s00723-014-0627-2 Finding the Reactive Electron in Paramagnetic Systems: A Critical Evaluation of Accuracies for EPR Spectroscopy and Density Functional Theory Using 1,3,5-Triphenyl Verdazyl Radical as a Testcase [Elektronische Daten] [Jessica Barilone, Frank Neese, Maurice van Gastel] One of the biggest challenges in studying catalytic reactions is characterizing intermediate states and identifying reaction pathways. Oftentimes, intermediate states with unpaired electrons are formed which provide an opportunity to study the compound via electron paramagnetic resonance (EPR). Combining EPR with density functional theory (DFT) represents a powerful synergistic approach to accomplish these goals. Once the catalytic intermediates and reaction pathway are known, rate-limiting steps critical to parameters like overpotential and turnover number may be identified and eliminated. In this study 1,3,5-triphenyl verdazyl is examined using continuous-wave-EPR, electron nuclear double resonance and DFT as an instructive example of how theory and experiment can complement each other to find the reactive electron. The methods and concomitant analysis have been presented in didactic fashion and with emphasis on the strengths and weaknesses of the methods. Springer-Verlag Wien, 2014 Barilone Jessica Max Planck Institute for Chemical Energy Conversion, Stiftstrasse 34-36, 45470, Mülheim an der Ruhr, Germany aut Neese Frank Max Planck Institute for Chemical Energy Conversion, Stiftstrasse 34-36, 45470, Mülheim an der Ruhr, Germany aut van Gastel Maurice Max Planck Institute for Chemical Energy Conversion, Stiftstrasse 34-36, 45470, Mülheim an der Ruhr, Germany aut Applied Magnetic Resonance Springer Vienna 46/2(2015-02-01), 117-139 0937-9347 46:2<117 2015 46 723 https://doi.org/10.1007/s00723-014-0627-2 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00723-014-0627-2 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Barilone Jessica Max Planck Institute for Chemical Energy Conversion, Stiftstrasse 34-36, 45470, Mülheim an der Ruhr, Germany aut NATIONALLICENCE 700 1- Neese Frank Max Planck Institute for Chemical Energy Conversion, Stiftstrasse 34-36, 45470, Mülheim an der Ruhr, Germany aut NATIONALLICENCE 700 1- van Gastel Maurice Max Planck Institute for Chemical Energy Conversion, Stiftstrasse 34-36, 45470, Mülheim an der Ruhr, Germany aut NATIONALLICENCE 773 0- Applied Magnetic Resonance Springer Vienna 46/2(2015-02-01), 117-139 0937-9347 46:2<117 2015 46 723