On the Electronic Structure of Molecular UO₂ in the Presence of Ar Atoms: Evidence for Direct U-Ar Bonding

Journal Article · Mon Mar 01 04:00:00 EST 2004 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/ja039933w· OSTI ID:1152377

Li, Jun; Bursten, Bruce E.; Andrews, Lester; Marsden, Colin J.

Calculations via scalar-relativistic density functional theory (DFT) and ab initio CCSD(T) methodologies are used to explore the possibility of direct interactions between molecular UO2 and Ar atoms. The ³H_g electronic state of UO₂, which is an excited state of the isolated molecule, exhibits significant bonding to Ar in the model complexes UO₂(Ar) and UO₂(Ar)₅. The calculated vibrational frequencies of ground-state ³Φ_u UO₂ and UO₂(Ar)₅ with an (fφ)¹(fδ)¹ electron configuration agree well with the observed frequencies of UO₂ in solid neon and solid argon, respectively. The results strongly suggest that the ground electron configuration of UO₂ changes from 5f¹7s¹ to 5f² when the matrix host is changed from neon to argon.

• Research Organization: Environmental Molecular Sciences Laboratory (EMSL)
• Sponsoring Organization: USDOE Office of Science (SC), Biological and Environmental Research (BER)
• OSTI ID: 1152377
• Journal Information: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 11 Vol. 126; ISSN 0002-7863
• Publisher: American Chemical Society (ACS)
• Country of Publication: United States
• Language: English