Cover Image

Observation of electron-transfer-mediated decay in aqueous solution

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 eith...

Full description

Saved in:
Bibliographic Details
Main Authors: Unger, Isaak (Author) , Cederbaum, Lorenz S. (Author) , Kryzhevoi, Nikolai V. (Author)
Format: Article (Journal)
Language:English
Published: 20 February 2017
In: Nature chemistry
Year: 2017, Volume: 9, Issue: 7, Pages: 708-714
ISSN:1755-4349
DOI:10.1038/nchem.2727
Online Access:Verlag, Pay-per-use, Volltext: http://dx.doi.org/10.1038/nchem.2727
Verlag, Pay-per-use, Volltext: https://www.nature.com/articles/nchem.2727
Get full text
Author Notes:Isaak Unger, Robert Seidel, Stephan Thürmer, Marvin N. Pohl, Emad F. Aziz, Lorenz S. Cederbaum, Eva Muchová, Petr Slavíček, Bernd Winter and Nikolai V. Kryzhevoi
Description
Summary: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.
Item Description:Gesehen am 04.10.2018
Physical Description:Online Resource
ISSN:1755-4349
DOI:10.1038/nchem.2727

Similar Items