Resonant X-ray photoelectron spectroscopy: identification of atomic contributions to valence states

Abstract

Valence electronic structure is crucial for understanding and predicting reactivity. Valence non-resonant X-ray photoelectron spectroscopy (NRXPS) provides a direct method for probing the overall valence electronic structure. However, it is often difficult to separate the varying contributions to NRXPS; for example, contributions of solutes in solvents or functional groups in complex molecules. In this work we show that valence resonant X-ray photoelectron spectroscopy (RXPS) is a vital tool for obtaining atomic contributions to valence states. We combine RXPS with NRXPS and density functional theory calculations to demonstrate the validity of using RXPS to identify atomic contributions for a range of solutes (both neutral and ionic) and solvents (both molecular solvents and ionic liquids). Furthermore, the one-electron picture of RXPS holds for all of the closed shell molecules/ions studied, although the situation for an open-shell metal complex is more complicated. The factors needed to obtain a strong RXPS signal are investigated in order to predict the types of systems RXPS will work best for; a balance of element electronegativity and bonding type is found to be important. Additionally, the dependence of RXPS spectra on both varying solvation environment and varying local-covalent bonding is probed. We find that RXPS is a promising fingerprint method for identifying species in solution, due to the spectral shape having a strong dependence on local-covalency but a weak dependence on the solvation environment.

Graphical abstract: Resonant X-ray photoelectron spectroscopy: identification of atomic contributions to valence states

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Article information

Article type
Paper
Submitted
07 Dec 2021
Accepted
16 Feb 2022
First published
16 Feb 2022
This article is Open Access
Creative Commons BY license

Faraday Discuss., 2022, Advance Article

Resonant X-ray photoelectron spectroscopy: identification of atomic contributions to valence states

J. M. Seymour, E. Gousseva, R. A. Bennett, A. I. Large, G. Held, D. Hein, G. Wartner, W. Quevedo, R. Seidel, C. Kolbeck, C. J. Clarke, R. M. Fogarty, R. A. Bourne, R. G. Palgrave, P. A. Hunt and K. R. J. Lovelock, Faraday Discuss., 2022, Advance Article , DOI: 10.1039/D1FD00117E

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