Strong electron correlation in UO2(-): a photoelectron spectroscopy and relativistic quantum chemistry study

The electronic structures of actinide systems are extremely complicated and pose considerable challenges both experimentally and theoretically because of significant electron correlation and relativistic effects. Here we report an investigation of the electronic structure and chemical bonding of uranium dioxides, UO2(-) and UO2, using photoelectron spectroscopy and relativistic quantum chemistry. The electron affinity of UO2 is measured to be 1.159(20) eV. Intense detachment bands are observed from the UO2(-) low-lying (7sσg)(2)(5fϕu)(1) orbitals and the more deeply bound O2p-based molecular orbitals which are separated by a large energy gap from the U-based orbitals. Surprisingly, numerous weak photodetachment transitions are observed in the gap region due to extensive two-electron transitions, suggesting strong electron correlations among the (7sσg)(2)(5fϕu)(1) electrons in UO2(-) and the (7sσg)(1)(5fϕu)(1) electrons in UO2. These observations are interpreted using multi-reference ab initio calculations with inclusion of spin-orbit coupling. The strong electron correlations and spin-orbit couplings generate orders-of-magnitude more detachment transitions from UO2(-) than expected on the basis of the Koopmans' theorem. The current experimental data on UO2(-) provide a long-sought opportunity to arbitrating various relativistic quantum chemistry methods aimed at handling systems with strong electron correlations.