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

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

doi:10.1016/j.cplett.2016.12.046

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

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

Research output: Contribution to journal › Article › Academic › peer-review

Abstract

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. 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.

Original language	English
Pages (from-to)	196-201
Number of pages	6
Journal	Chemical Physics Letters
Volume	669
DOIs	https://doi.org/10.1016/j.cplett.2016.12.046
Publication status	Published - Feb 2017

Keywords

Transition-metal ion
Aqueous solution
Covalent interaction
Resonant Inelastic X-ray Scattering
Ligand-field state
Charge-transfer state

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

abstract = "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. 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.",

keywords = "Transition-metal ion, Aqueous solution, Covalent interaction, Resonant Inelastic X-ray Scattering, Ligand-field state, Charge-transfer state",

author = "K. Kunnus and I. Josefsson and S. Schreck and W. Quevedo and P.S. Miedema and S. Techert and {de Groot}, F.M.F. and A. F{\"o}hlisch and M. Odelius and Ph Wernet",

year = "2017",

month = feb,

doi = "10.1016/j.cplett.2016.12.046",

language = "English",

volume = "669",

pages = "196--201",

journal = "Chemical Physics Letters",

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TY - JOUR

T1 - Quantifying covalent interactions with resonant inelastic soft X-ray scattering: Case study of Ni2+ aqua complex

AU - Kunnus, K.

AU - Josefsson, I.

AU - Schreck, S.

AU - Quevedo, W.

AU - Miedema, P.S.

AU - Techert, S.

AU - de Groot, F.M.F.

AU - Föhlisch, A.

AU - Odelius, M.

AU - Wernet, Ph

PY - 2017/2

Y1 - 2017/2

N2 - 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. 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.

AB - 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. 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.

KW - Transition-metal ion

KW - Aqueous solution

KW - Covalent interaction

KW - Resonant Inelastic X-ray Scattering

KW - Ligand-field state

KW - Charge-transfer state

U2 - 10.1016/j.cplett.2016.12.046

DO - 10.1016/j.cplett.2016.12.046

M3 - Article

SN - 0009-2614

VL - 669

SP - 196

EP - 201

JO - Chemical Physics Letters

JF - Chemical Physics Letters

ER -

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

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Keywords

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