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Real Time Determination of the Electronic Structure of Unstable Reaction Intermediates during Au2O3 Reduction

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Paul Scherrer Institut, Villigen, Switzerland
Institute of Physics, Jan Kochanowski University, Kielce, Poland
§ LSU Group, École Polytechnique Fédérale de Lausanne (EPFL), Lausanne, Switzerland
Department for Chemical and Bioengineering, ETH Zurich, Zurich, Switzerland
# Department of Physics, University of Fribourg, Fribourg, Switzerland
Department of Chemistry, University of Aveiro, Aveiro, Portugal
School of Physics, The University of Sydney, Sydney, Australia
*E-mail: [email protected] (J. Szlachetko).
*E-mail: [email protected] (C. Stampfl).
Cite this: J. Phys. Chem. Lett. 2014, 5, 1, 80–84
Publication Date (Web):December 6, 2013
Copyright © 2013 American Chemical Society

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Chemical reactions are always associated with electronic structure changes of the involved chemical species. Determining the electronic configuration of an atom allows probing its chemical state and gives understanding of the reaction pathways. However, often the reactions are too complex and too fast to be measured at in situ conditions due to slow and/or insensitive experimental techniques. A short-lived Au2O compound has been detected for the first time under in situ conditions during the temperature-programmed reduction of Au2O3. A time-resolved resonant inelastic X-ray scattering experiment (RIXS) allowed the determination of changes in the Au electronic structure, enabling a better understanding of the reaction mechanism of Au(III) reduction. On the basis of time-resolved RIXS data analysis combined with genetic algorithm methodology, we determined the electronic structure of the metastable Au2O intermediate species. The data analysis showed a notably larger value for the lattice constant of the intermediate Au as compared to the theoretical predictions. With support of DFT calculations, we found that such a structure may indeed be formed and that the expanded lattice constant is due to the termination of Au2O on the Au2O3 structure.

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