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Resonant electron spectroscopy: identification of atomic contributions to valence states

DOI: 10.1039/D1FD00117E DOI Help

Authors: Jake M. Seymour (University of Reading) , Ekaterina Gousseva (University of Reading) , Alex Large (Helmholtz-Zentrum Berlin für Materialien und Energie (HZB)) , Georg Held (Diamond Light Source) , Dennis Hein (Helmholtz-Zentrum Berlin für Materialien und Energie (HZB)) , Garlef Wartner (Helmholtz-Zentrum Berlin für Materialien und Energie (HZB)) , Wilson Quevedo (Helmholtz-Zentrum Berlin für Materialien und Energie (HZB)) , Robert Seidel (Helmholtz-Zentrum Berlin für Materialien und Energie (HZB)) , Claudia Kolbeck (Fritz-Haber-Institut der Max-Planck-Gesellschaft) , Coby J. Clarke (University of Nottingham) , Richard M. Fogarty (Imperial College London) , Richard A. Bourne (University of Leeds) , Roger A. Bennett (University of Reading) , Robert G. Palgrave (University College London) , Patricia A. Hunt (Victoria University of Wellington) , Kevin R. J. Lovelock (University of Reading)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Faraday Discussions

State: Published (Approved)
Published: February 2022
Diamond Proposal Number(s): 24304 , 25929

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. 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 solvation environment.

Subject Areas: Chemistry, Technique Development

Instruments: B07-C-Versatile Soft X-ray beamline: Ambient Pressure XPS and NEXAFS

Other Facilities: I311 at MAX-lab; SOL3PES at BESSY II

Added On: 10/03/2022 08:56

Discipline Tags:

Physical Chemistry Technique Development - Chemistry Chemistry

Technical Tags:

Spectroscopy X-ray Photoelectron Spectroscopy (XPS)