Photoelectron spectroscopy and the electronic structure of the uranyl tetrachloride dianion: UO 2Cl 42-

Abstract

The uranyl tetrachloride dianion (UO 2Cl 42-) is observed in the gas phase using electrospray ionization and investigated by photoelectron spectroscopy and relativistic quantum chemical calculations. Photoelectron spectra of UO 2Cl 42- are obtained at various photon energies and congested spectral features are observed. The free UO 2Cl 42- dianion is found to be highly stable with an adiabatic electron binding energy of 2.40 eV. Ab initio calculations are carried out and used to interpret the photoelectron spectra and elucidate the electronic structure of UO 2Cl 42-. The calculations show that the frontier molecular orbitals in UO 2Cl 42- are dominated by the ligand Cl 3p orbitals, while the U-O bonding orbitals are much more stable. The electronic structure of UO 2Cl 42- is compared with that of the recently reported UO 2F 42- P. D. Dau, J. Su, H. T. Liu, J. B. Liu, D. L. Huang, J. Li, and L. S. Wang, Chem. Sci. 3 1137 (2012). The electron binding energy of UO 2Cl 42- is found to be 1.3 eV greater than that of UO 2F 42-. The differences in the electronic stability and electronic structure between UO 2Cl 42- and UO 2F 42- are discussed. © 2012 American Institute of Physics.