skip to main content

DOE PAGESDOE PAGES

Title: Quantifying covalent interactions with resonant inelastic soft X-ray scattering: Case study of Ni 2+ aqua complex

We analyze the effects of covalent interactions in Ni 2p3d resonant inelastic X-ray scattering (RIXS) spectra from aqueous Ni 2+ 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 L 3-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 L 3-edge can be utilized to quantify covalency in Ni complexes without the use of external references or simulations.
Authors:
 [1] ;  [2] ;  [1] ;  [3] ;  [3] ;  [4] ;  [5] ;  [1] ;  [2] ;  [3]
  1. Helmholtz-Zentrum Berlin fur Materialien und Energie, Berlin (Germany); Univ. Potsdam, Potsdam (Germany)
  2. Stockholm Univ., Stockholm (Sweden)
  3. Helmholtz-Zentrum Berlin fur Materialien und Energie, Berlin (Germany)
  4. Max Planck Institute for Biophysical Chemistry, Gottingen (Germany); Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)
  5. Utrecht Univ., Utrecht (Netherlands)
Publication Date:
Grant/Contract Number:
AC02-76SF00515
Type:
Accepted Manuscript
Journal Name:
Chemical Physics Letters
Additional Journal Information:
Journal Volume: 669; Journal Issue: C; Journal ID: ISSN 0009-2614
Publisher:
Elsevier
Research Org:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; transition-metal ion; aqueous solution; covalent interaction; resonant inelastic X-ray scattering; ligand-field state; charge-transfer state
OSTI Identifier:
1347974
Alternate Identifier(s):
OSTI ID: 1349417

Kunnus, K., Josefsson, I., Schreck, S., Quevedo, W., Miedema, P. S., Techert, S., de Groot, F. M. F., Föhlisch, A., Odelius, M., and Wernet, Ph.. Quantifying covalent interactions with resonant inelastic soft X-ray scattering: Case study of Ni2+ aqua complex. United States: N. p., Web. doi:10.1016/j.cplett.2016.12.046.
Kunnus, K., Josefsson, I., Schreck, S., Quevedo, W., Miedema, P. S., Techert, S., de Groot, F. M. F., Föhlisch, A., Odelius, M., & Wernet, Ph.. Quantifying covalent interactions with resonant inelastic soft X-ray scattering: Case study of Ni2+ aqua complex. United States. doi:10.1016/j.cplett.2016.12.046.
Kunnus, K., Josefsson, I., Schreck, S., Quevedo, W., Miedema, P. S., Techert, S., de Groot, F. M. F., Föhlisch, A., Odelius, M., and Wernet, Ph.. 2016. "Quantifying covalent interactions with resonant inelastic soft X-ray scattering: Case study of Ni2+ aqua complex". United States. doi:10.1016/j.cplett.2016.12.046. https://www.osti.gov/servlets/purl/1347974.
@article{osti_1347974,
title = {Quantifying covalent interactions with resonant inelastic soft X-ray scattering: Case study of Ni2+ aqua complex},
author = {Kunnus, K. and Josefsson, I. and Schreck, S. and Quevedo, W. and Miedema, P. S. and Techert, S. and de Groot, F. M. F. and Föhlisch, A. and Odelius, M. and Wernet, Ph.},
abstractNote = {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.},
doi = {10.1016/j.cplett.2016.12.046},
journal = {Chemical Physics Letters},
number = C,
volume = 669,
place = {United States},
year = {2016},
month = {12}
}