期刊
CHEMICAL SCIENCE
卷 5, 期 1, 页码 351-359出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c3sc52030g
关键词
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资金
- Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences, U.S. Department of Energy at LBNL [DE-AC0205CH11231]
- Heavy Element Chemistry Program at LANL [DE-AC5206NA25396]
- Office of Science, Office of Basic Energy Sciences Division of Chemical Sciences, Geosciences, and Biosciences
- Condensed Phase and Interfacial Molecular Sciences Program of the aforementioned Division of the U.S. Department of Energy at LBNL [DE-AC02-05CH11231]
- Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy [DE-AC02-05CH11231]
- LBNL by the Berkeley Actinide Postdoctoral Fellowship
- LANL by a Glenn T. Seaborg Institute Postdoctoral Fellowship
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 delta-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 phi-orbital interactions has been provided by the C K-edge XAS analysis of thorocene; however, phi-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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