Faculté des sciences

Real time determination of the electronic structure of unstable reaction intermediates during Au₂O₃ Reduction

Szlachetko, Jakub ; Sá, Jacinto ; Nachtegaal, Maarten ; Hartfelder, Urs ; Dousse, Jean-Claude ; Hoszowska, Joanna ; Fernandes, Daniel Luis Abreu ; Shi, Hongqing ; Stampfl, Catherine

In: The Journal of Physical Chemistry Letters, 2014, vol. 5, no. 1, p. 80–84

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... More

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    Summary
    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.during Au₂O₃ Reduction