Electrospray mass spectrum for UO2F3 −, UF5 −, and UF6 −.
Photoelectron spectra of UF5 − at (a) 275 nm (4.508 eV), (b) 266 nm (4.661 eV), (c) 245 nm (5.061 eV), and (d) 213 nm (5.821 eV). HB stands for hot band transitions.
Frank-Condon simulation (blue solid line) for the ground-state detachment transition of UF5 − using PESCAL (Ref. 84) compared with the 245 nm PES spectrum (dotted line). The vertical lines are the calculated Frank-Condon factors (blue: transitions from the vibrational ground state; red: transitions from vibrational hot bands).
Molecular orbital energy levels of UF5 − from SR-DFT/PBE calculation. The 2b2 and 8a1 orbitals are singly occupied and the other higher lying 5f orbitals are unoccupied.
The frontier molecular orbitals of UF5 − at SR-DFT/PBE level. See Fig. 4 for the energy ordering. The two singly occupied molecular orbitals are 8a1 and 2b2, and the 8e, 7e, and 4b1 orbitals are unoccupied.
Calculated photoelectron spectra (red) compared with the experimental photoelectron spectrum of UF5 − at 213 nm (blue). (a) Only the ground-state transition is used. (b) Both the detachment transitions to the ground and first excited state of UF5 are included. The contribution by the excited state is ∼9%.
The adiabatic (ADE) and vertical (VDE) detachment energies for UF6 − and UF5 − calculated at different levels of theory and comparison with experimental values for UF5 −. All energies are in eV.
Optimized geometrical parameters of UF6 − and UF5 − and their neutrals at both DFT and CCSD(T) levels of theory.
Parameters for the Franck-Condon calculations for the two detachment bands of UF5 −.
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