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Download fileMetal–Metal Bonding in Actinide Dimers: U2 and U2–
journal contribution
posted on 2021-10-05, 19:15 authored by Sandra
M. Ciborowski, Abhishek Mitra, Rachel M. Harris, Gaoxiang Liu, Prachi Sharma, Navneet Khetrapal, Moritz Blankenhorn, Laura Gagliardi, Kit H. BowenUnderstanding direct metal–metal
bonding between actinide
atoms has been an elusive goal in chemistry for years. We report for
the first time the anion photoelectron spectrum of U2–. The threshold of the lowest electron binding energy
(EBE) spectral band occurs at 1.0 eV, which corresponds to the electron
affinity (EA) of U2, whereas the vertical detachment energy
of U2– is found at EBE ∼ 1.2 eV.
Electronic structure calculations on U2 and U2– were carried out with state-of-the-art theoretical
methods. The computed values of EA(U2) and EA(U) and the
difference between the computed dissociation energies of U2 and U2– are found to be internally
consistent and consistent with experiment. Analysis of the bonds in
U2 and U2– shows that while
U2 has a formal quintuple bond, U2– has a quadruple bond, even if the effective bond orders differ only
by 0.5 unit instead of one unit. The resulting experimental-computational
synergy elucidates the nature of metal–metal bonding in U2 and U2–.
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vertical detachment energyspectral band occurselectronic structure calculationscomputational synergy elucidatesart theoretical methodsanion photoelectron spectrumformal quintuple bondcomputed dissociation energies5 unit instead2 </ subebe ∼ 1ea ( uquadruple bondone unitcomputed values2 evresulting experimentalfirst timeelusive goalelectron affinityactinide dimersactinide atoms