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Metal–Metal Bonding in Actinide Dimers: U2 and U2

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journal contribution
posted on 05.10.2021, 19:15 authored by Sandra M. Ciborowski, Abhishek Mitra, Rachel M. Harris, Gaoxiang Liu, Prachi Sharma, Navneet Khetrapal, Moritz Blankenhorn, Laura Gagliardi, Kit H. Bowen
Understanding 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.