We thank V.N. Strocov, P.S. Peijzel, and K.P. de Jong for support and discussions, and NWO-CW VICI for financial support. XAS/RXES were performed at the ADRESS beamline of the SLS using the SAXES instrument jointly built by PSI, Switzerland and Politecnico di Milano, Italy.
A Multispectroscopic Study of 3 d Orbitals in Cobalt Carboxylates: The High Sensitivity of 2p3d Resonant X-ray Emission Spectroscopy to the Ligand Field†
Article first published online: 6 DEC 2012
Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Angewandte Chemie International Edition
Volume 52, Issue 4, pages 1170–1174, January 21, 2013
How to Cite
van Schooneveld, M. M., Gosselink, R. W., Eggenhuisen, T. M., Al Samarai, M., Monney, C., Zhou, K. J., Schmitt, T. and de Groot, F. M. F. (2013), A Multispectroscopic Study of 3 d Orbitals in Cobalt Carboxylates: The High Sensitivity of 2p3d Resonant X-ray Emission Spectroscopy to the Ligand Field . Angew. Chem. Int. Ed., 52: 1170–1174. doi: 10.1002/anie.201204855
- Issue published online: 15 JAN 2013
- Article first published online: 6 DEC 2012
- Manuscript Received: 21 JUN 2012
- Funded Access
- NWO-CW VICI
- 1aThe theory of transition metal ions, Cambridge University Press, Cambridge, 1964;,
- 1bModern Aspects of Ligand Field Theory, North-Holland, Amsterdam, 1971;,
- 1cInorganic electronic structure and spectroscopy—Methodology, Wiley, Hoboken, 2006., ,
- 5aA detailed experimental section is given in the Supporting Information.
- 8cThe Theory of Atomic Structure and Spectra, University of California Press, Berkeley, 1981;,
- 9Other effects that in general may further split and shift the manifolds over a relatively small range of 0.1–0.2 eV, are the 3d spin-orbit coupling and magnetic superexchange interactions. In inorganic complexes the distance between metal ions is relatively large and the visible spectral effects of magnetic interactions (including collective ones) can be neglected.
- 10This holds for weak and strong ligand fields. It does not hold for the rare condition of very weak intra-atomic interactions (the peaks in region B would shift to region A).
- 11The weak ligand field implies that the lowest energy excitations could be one-electron excitations for 3d2, 3d3, 3d4, 3d6, 3d7, and 3d8 systems in all symmetries.
- 14We use the spectroscopic convention to put the initial state at the right side of a transition.