KIT | KIT-Bibliothek | Impressum
Open Access Logo
§
Volltext
URN: urn:nbn:de:swb:90-721399

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.

Abstract:
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 M4,5 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.


Zugehörige Institution(en) am KIT Institut für Katalyseforschung und -Technologie (IKFT)
Institut für Nukleare Entsorgung (INE)
Institut für Technische Chemie und Polymerchemie (ITCP)
Publikationstyp Zeitschriftenaufsatz
Jahr 2017
Sprache Englisch
Identifikator ISSN: 2041-1723
URN: urn:nbn:de:swb:90-721399
KITopen ID: 1000072139
HGF-Programm 32.01.04; LK 01
Erschienen in Nature Communications
Band 8
Seiten 16053
Bemerkung zur Veröffentlichung Gefördert durch den KIT-Publikationsfonds
KIT – Die Forschungsuniversität in der Helmholtz-Gemeinschaft KITopen Landing Page