From ligand fields to molecular orbitals: Probing the local valence electronic 
structure of Ni2+ in aqueous solution with resonant inelastic X-ray scattering.

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

doi:10.1021/jp4100813

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From ligand fields to molecular orbitals: Probing the local valence electronic structure of Ni2+ in aqueous solution with resonant inelastic X-ray scattering.

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Techert, S.
Research Group of Structural Dynamics of (Bio)Chemical Systems, MPI for biophysical chemistry, Max Planck Society;

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Zitation

Kunnus, K., Josefsson, I., Schreck, S., Quevedo, W., Miedema, P. S., Techert, S., et al. (2013). From ligand fields to molecular orbitals: Probing the local valence electronic structure of Ni2+ in aqueous solution with resonant inelastic X-ray scattering. Journal of Physical Chemistry B, 117(51), 16512-16521. doi:10.1021/jp4100813.

Zitierlink: https://hdl.handle.net/11858/00-001M-0000-0015-368C-2

Zusammenfassung

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.