4 years ago

Sensitivity of Electron Transfer Mediated Decay to Ion Pairing

Sensitivity of Electron Transfer Mediated Decay to Ion Pairing
Bernd Winter, Petr Slavíček, Uwe Hergenhahn, Bernd Abel, Robert Seidel, Evgeny Lugovoy, Clemens Richter, Marvin N. Pohl, Emad F. Aziz
Ion pairing in electrolyte solutions remains a topic of discussion despite a long history of research. Very recently, nearest-neighbor mediated electronic de-excitation 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.

Publisher URL: http://dx.doi.org/10.1021/acs.jpcb.7b06061

DOI: 10.1021/acs.jpcb.7b06061

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