From Ligand Fields to Molecular Orbitals: Probing the Local Valence Electronic Structure of Ni2+ in Aqueous Solution with Resonant Inelastic X-ray Scattering

Kristjan Kunnus, Ida Josefsson, Simon Schreck, Wilson Quevedo, Piter S. Miedema, Simone Techert, Frank M. F. de Groot, Michael Odelius, Philippe Wernet*, Alexander Foehlisch

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

Abstract

Bonding of the Ni2+(aq) complex is investigated with an unprecedented combination of resonant inelastic X-ray scattering (RIXS) measurements and ab initio calculations at the Ni L absorption edge. The spectra directly reflect the relative energies of the ligand-field and charge-transfer valence-excited states. They give element-specific access with atomic resolution to the ground-state electronic structure of the complex and allow quantification of ligand-field strength and 3d-3d electron correlation interactions in the Ni2+(aq) complex. The experimentally determined ligand-field strength is 10Dq = 1.1 eV. This and the Racah parameters characterizing 3d-3d Coulomb interactions B = 0.13 eV and C = 0.42 eV as readily derived from the measured energies match very well with the results from UV-vis spectroscopy. Our results demonstrate how L-edge RIXS can be used to complement existing spectroscopic tools for the investigation of bonding in 3d transition-metal coordination compounds in solution. The ab initio RASPT2 calculation is successfully used to simulate the L-edge RIXS spectra.

Original languageEnglish
Pages (from-to)16512-16521
Number of pages10
JournalJournal of Physical Chemistry. B
Volume117
Issue number51
DOIs
Publication statusPublished - 26 Dec 2013

Funding

We gratefully acknowledge the continuous support by the BESSYII staff. Portions of the presented research were funded by the Helmholtz Virtual Institute "Dynamic Pathways in Multidimensional Landscapes". This work was supported by the Swedish Research Council.

Keywords

  • TRANSITION-METAL IONS
  • PARTIAL FLUORESCENCE YIELD
  • AB-INITIO CALCULATIONS
  • L-EDGE
  • ABSORPTION-SPECTROSCOPY
  • EMISSION SPECTROSCOPY
  • ATOMIC MULTIPLET
  • WATER EXCHANGE
  • SPECTRA
  • DFT

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