New evidence for 5f covalency in actinocenes determined from carbon K-edge XAS and electronic structure theory†
* Corresponding authors
a Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA
E-mail:dkshuh@lbl.gov
b Los Alamos National Laboratory, Los Alamos, NM 87545, USA
E-mail:erb@lanl.gov,stosh@lanl.gov,rlmartin@lanl.gov
Abstract
Evidence for metal–carbon orbital mixing in thorocene and uranocene was determined from DFT calculations and carbon K-edge X-ray absorption spectra (XAS) collected with a scanning transmission X-ray microscope (STXM). Both the experimental and computational results showed that the 5f orbitals engaged in significant δ-type mixing with the C8H82− ligands, which increased as the 5f orbitals dropped in energy on moving from Th4+ to U4+. The first experimental evidence for extensive ϕ-orbital interactions has been provided by the C K-edge XAS analysis of thorocene; however, ϕ-type covalency in uranocene was negligible. The results highlighted two contrasting trends in orbital mixing from one pair of highly symmetric molecules, and showed that covalency does not increase uniformly for different molecular orbital interactions with later actinides.
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Article information
- Article type
- Edge Article
- Submitted
- 19 Jul 2013
- Accepted
- 30 Sep 2013
- First published
- 05 Nov 2013
Permissions
New evidence for 5f covalency in actinocenes determined from carbon K-edge XAS and electronic structure theory
S. G. Minasian, J. M. Keith, E. R. Batista, K. S. Boland, D. L. Clark, S. A. Kozimor, R. L. Martin, D. K. Shuh and T. Tyliszczak,Chem. Sci., 2014, 5, 351DOI: 10.1039/C3SC52030G
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