From Ligand Fields to Molecular Orbitals: Probing the Local Valence Electronic Structure of Ni2+ in Aqueous Solutions with Resonant Inelastic X-ray Scattering
Number of Authors: 10
2013 (English)In: Journal of Physical Chemistry B, ISSN 1520-6106, E-ISSN 1520-5207, Vol. 117, 16512-16521 p.Article in journal (Refereed) Published
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.
Place, publisher, year, edition, pages
2013. Vol. 117, 16512-16521 p.
Research subject Physics
IdentifiersURN: urn:nbn:se:su:diva-119836DOI: 10.1021/jp4100813ISI: 000329331800016OAI: oai:DiVA.org:su-119836DiVA: diva2:848759