On the electronic structure of molecular UO2 in the presence of Ar atoms: evidence for direct U-Ar bonding.

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 3Hg 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 3Phiu UO2 and UO2(Ar)5 with an (fphi)1(fdelta)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.