Nature Chemistry
Nature Chemistry
5 years ago

Observation of electron-transfer-mediated decay in aqueous solution

Observation of electron-transfer-mediated decay in aqueous solution
Eva Muchová, Petr Slavíček, Stephan Thürmer, Marvin N. Pohl, Robert Seidel, Nikolai V. Kryzhevoi, Lorenz S. Cederbaum, Isaak Unger, Emad F. Aziz, Bernd Winter
Photoionization is at the heart of X-ray photoelectron spectroscopy (XPS), which gives access to important information on a sample's local chemical environment. Local and non-local electronic decay after photoionization—in which the refilling of core holes results in electron emission from either the initially ionized species or a neighbour, respectively—have been well studied. However, electron-transfer-mediated decay (ETMD), which involves the refilling of a core hole by an electron from a neighbouring species, has not yet been observed in condensed phase. Here we report the experimental observation of ETMD in an aqueous LiCl solution by detecting characteristic secondary low-energy electrons using liquid-microjet soft XPS. Experimental results are interpreted using molecular dynamics and high-level ab initio calculations. We show that both solvent molecules and counterions participate in the ETMD processes, and different ion associations have distinctive spectral fingerprints. Furthermore, ETMD spectra are sensitive to coordination numbers, ion–solvent distances and solvent arrangement.

Publisher URL: http://dx.doi.org/10.1038/nchem.2727

DOI: 10.1038/nchem.2727

You might also like
Discover & Discuss Important Research

Keeping up-to-date with research can feel impossible, with papers being published faster than you'll ever be able to read them. That's where Researcher comes in: we're simplifying discovery and making important discussions happen. With over 19,000 sources, including peer-reviewed journals, preprints, blogs, universities, podcasts and Live events across 10 research areas, you'll never miss what's important to you. It's like social media, but better. Oh, and we should mention - it's free.

  • Download from Google Play
  • Download from App Store
  • Download from AppInChina

Researcher displays publicly available abstracts and doesn’t host any full article content. If the content is open access, we will direct clicks from the abstracts to the publisher website and display the PDF copy on our platform. Clicks to view the full text will be directed to the publisher website, where only users with subscriptions or access through their institution are able to view the full article.