Photoelectron spectra of UO2Cl4 2− at (a) 266 nm (4.661 eV), (b) 245 nm (5.061 eV), (c) 213 nm (5.821 eV), and (d) 157 nm (7.866 eV).
The SR and SO energy levels of the frontier occupied orbitals of UO2Cl4 2− calculated at the DFT/PBE level. The 1a 1g, 1e g, 1e u, and 1a 2u orbitals correspond to U–O bonding orbitals in UO2 2+ and all the other orbitals mainly belong to Cl 3p lone pairs.
The contour diagrams of the occupied valence orbitals of UO2Cl4 2− at the DFT/PBE level. The 2a 2u and 1a 2g orbitals are close in energy and compete for the HOMO.
Simulated photoelectron spectra of UO2Cl4 2− from (a) CASSCF/CCSD(T)/SO calculations and (b) CASSCF/CR-EOM-CCSD(T)/SO calculations, in comparison with the 157 nm experimental data. The simulated spectra were generated by fitting a Gaussian of 0.06 eV width and unit area to each calculated VDE. The Gaussian width is chosen to be comparable to instrumental resolution at 157 nm. See Table IV for the detailed detachment channels.
Observed adiabatic (ADE) and vertical (VDE) detachment energies for UO2Cl4 2− compared to calculations at different levels of theory.a All energies are in eV.
Optimized geometrical parameters of UO2Cl4 2− and UO2Cl4 − at the scalar relativistic level.
Calculated VDEs and the corresponding spinors of UO2Cl4 2− from the SO-DFT/PBE level.
Calculated VDEs and the corresponding MOs of UO2Cl4 2− at the CASSCF/CCSD(T)/SO and CASSCF/CR-EOM-CCSD(T)/SO levels.
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