The role of the 5f valence orbitals of early actinides in chemical bonding

Vitova, T.; Pidchenko, I.; Fellhauer, D.; Bagus, P. S.; Joly, Y.; Pruessmann, T.; Bahl, S.; Gonzalez-Robles, E.; Rothe, J.; Altmaier, M.; Denecke, M. A.; Geckeis, H.

doi:10.1038/ncomms16053

Title: The role of the 5f valence orbitals of early actinides in chemical bonding

Journal Article · Thu Jul 06 00:00:00 EDT 2017 · Nature Communications

DOI:https://doi.org/10.1038/ncomms16053· OSTI ID:1623897

Vitova, T. ^[1]; Pidchenko, I. ^[1]; Fellhauer, D. ^[1]; Bagus, P. S. ^[2]; Joly, Y. ^[3]; Pruessmann, T. ^[1]; Bahl, S. ^[1]; Gonzalez-Robles, E. ^[1]; Rothe, J. ^[1]; Altmaier, M. ^[1]; Denecke, M. A. ^[1]; Geckeis, H. ^[1]

Karlsruhe Inst. of Technology (KIT) (Germany). Inst. for Nuclear Waste Disposal (INE)
Univ. of North Texas, Denton, TX (United States). Dept. of Chemistry
Univ. Grenoble Alpes (France). Inst. NEEL; Centre National de la Recherche Scientifique (CNRS), Grenoble (France). Inst. NEEL

One of the long standing debates in actinide chemistry is the level of localization and participation of the actinide 5f valence orbitals in covalent bonds across the actinide series. Here we illuminate the role of the 5f valence orbitals of uranium, neptunium and plutonium in chemical bonding using advanced spectroscopies: actinide M_4,5 HR-XANES and 3d4f RIXS. Results reveal that the 5f orbitals are active in the chemical bonding for uranium and neptunium, shown by significant variations in the level of their localization evidenced in the spectra. In contrast, the 5f orbitals of plutonium appear localized and surprisingly insensitive to different bonding environments. We envisage that this report of using relative energy differences between the 5fδ/φ and 5fπ*/5fσ* orbitals as a qualitative measure of overlap-driven actinyl bond covalency will spark activity, and extend to numerous applications of RIXS and HR-XANES to gain new insights into the electronic structures of the actinide elements.

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Research Organization:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; Helmholtz Association of German Research Centers

Grant/Contract Number:: AC05-76RL01830; VH-NG-734

OSTI ID:: 1623897

Journal Information:: Nature Communications, Vol. 8, Issue 1; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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