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Sensitivity of Electron Transfer Mediated Decay to Ion Pairing

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Pohl,  Marvin Nicolas
Molecular Physics, Fritz Haber Institute, Max Planck Society;
Helmholtz-Zentrum Berlin für Materialien und Energie, Methods for Material Development;
Department of Physics, Freie Universität Berlin;

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Winter,  Bernd
Molecular Physics, Fritz Haber Institute, Max Planck Society;

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Pohl, M. N., Richter, C., Lugovoy, E., Seidel, R., Slavíček, P., Aziz, E. F., et al. (2017). Sensitivity of Electron Transfer Mediated Decay to Ion Pairing. The Journal of Physical Chemistry B, 121(32), 7709-7714. doi:10.1021/acs.jpcb.7b06061.


Cite as: http://hdl.handle.net/11858/00-001M-0000-002D-89E8-E
Abstract
Ion pairing in electrolyte solutions remains a topic of discussion despite a long history of research. Very recently, nearest-neighbor mediated electronic deexcitation processes of core hole vacancies (Electron Transfer Mediated Decay, ETMD) were proposed to carry a spectral fingerprint of local solvation structure and in particular of contact ion pairs. Here, for the first time, we apply electron–electron coincidence detection to a liquid microjet, and record ETMD spectra of Li 1s vacancies in aqueous solutions of lithium chloride (LiCl) in direct comparison to lithium acetate (LiOAc). A change in the ETMD spectrum dependent on the electrolyte anion identity is observed for 4.5 M salt concentration. We discuss these findings within the framework of the formation and presence of contact ion pairs and the unique sensitivity of ETMD spectroscopy to ion pairing.