- 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 isBonding 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.…
MetadatenVerfasserangaben: | Kristjan KunnusORCiD, Ida Josefsson, Simon Schreck, Wilson Quevedo, Piter S. Miedema, Simone Techert, Frank M. F. de Groot, Michael OdeliusORCiD, Philippe Wernet, Alexander FöhlischORCiDGND |
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DOI: | https://doi.org/10.1021/jp4100813 |
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ISSN: | 1520-6106 |
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Titel des übergeordneten Werks (Englisch): | The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces & biophysical chemistry |
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Verlag: | American Chemical Society |
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Verlagsort: | Washington |
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Publikationstyp: | Wissenschaftlicher Artikel |
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Sprache: | Englisch |
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Jahr der Erstveröffentlichung: | 2013 |
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Erscheinungsjahr: | 2013 |
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Datum der Freischaltung: | 26.03.2017 |
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Band: | 117 |
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Ausgabe: | 51 |
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Seitenanzahl: | 10 |
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Erste Seite: | 16512 |
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Letzte Seite: | 16521 |
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Fördernde Institution: | Helmholtz Virtual Institute |
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Organisationseinheiten: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Physik und Astronomie |
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Peer Review: | Referiert |
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