Quantifying covalent interactions with resonant inelastic soft X-ray scattering: Case study of Ni2+ aqua complex

Kunnus, K.; Josefsson, I.; Schreck, S.; Quevedo, W.; Miedema, P. S.; Techert, S.; de Groot, F. M. F.; Föhlisch, A.; Odelius, M.; Wernet, Ph.

doi:10.1016/j.cplett.2016.12.046

Title: Quantifying covalent interactions with resonant inelastic soft X-ray scattering: Case study of Ni²⁺ aqua complex

Journal Article · Thu Dec 22 23:00:00 EST 2016 · Chemical Physics Letters

DOI: https://doi.org/10.1016/j.cplett.2016.12.046 · OSTI ID:1347974

Kunnus, K. ^[1]; Josefsson, I. ^[2]; Schreck, S. ^[1]; Quevedo, W. ^[3]; Miedema, P. S. ^[3]; Techert, S. ^[4]; de Groot, F. M. F. ^[5]; Föhlisch, A. ^[1]; Odelius, M. ^[2]; Wernet, Ph. ^[3]

Helmholtz-Zentrum Berlin fur Materialien und Energie, Berlin (Germany); Univ. Potsdam, Potsdam (Germany)
Stockholm Univ., Stockholm (Sweden)
Helmholtz-Zentrum Berlin fur Materialien und Energie, Berlin (Germany)
Max Planck Institute for Biophysical Chemistry, Gottingen (Germany); Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)
Utrecht Univ., Utrecht (Netherlands)

We analyze the effects of covalent interactions in Ni 2p3d resonant inelastic X-ray scattering (RIXS) spectra from aqueous Ni²⁺ ions and find that the relative RIXS intensities of ligand-to-metal charge-transfer final states with respect to the ligand-field final states reflect the covalent mixing between Ni 3d and water orbitals. Specifically, the experimental intensity ratio at the Ni L₃-edge allows to determine that the Ni 3d orbitals have on average 5.5% of water character. Here, we propose that 2p3d RIXS at the Ni L₃-edge can be utilized to quantify covalency in Ni complexes without the use of external references or simulations.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1347974

Journal Information:: Chemical Physics Letters, Journal Name: Chemical Physics Letters Journal Issue: C Vol. 669; ISSN 0009-2614

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Strain analysis from M-edge resonant inelastic X-ray scattering of nickel oxide films Miedema, P. S.; Thielemann-Kühn, N.; Calafell, I. Alonso Physical Chemistry Chemical Physics, Vol. 21, Issue 38 https://doi.org/10.1039/c9cp03593a	journal	January 2019
Strain analysis from M-edge resonant inelastic X-ray scattering of nickel oxide films Miedema, P. S.; Thielemann-Kühn, N.; Calafell, I. Alonso Deutsches Elektronen-Synchrotron, DESY, Hamburg https://doi.org/10.3204/pubdb-2019-03239	text	January 2019

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
aqueous solution
charge-transfer state
covalent interaction
ligand-field state
resonant inelastic X-ray scattering
transition-metal ion

Title: Quantifying covalent interactions with resonant inelastic soft X-ray scattering: Case study of Ni2+ aqua complex

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References (42)

Cited By (2)

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Title: Quantifying covalent interactions with resonant inelastic soft X-ray scattering: Case study of Ni²⁺ aqua complex