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A combined photoelectron spectroscopy and relativistic ab initio studies of the electronic structures of UFO and UFO–

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4942188· OSTI ID:1469686
 [1];  [2];  [2];  [2];  [3];  [4];  [4];  [2];  [5]
  1. Tsinghua Univ., Beijing (China); Washington State Univ., Pullman, WA (United States)
  2. Brown Univ., Providence, RI (United States)
  3. Chinese Academy of Sciences, Shanghai (China)
  4. Washington State Univ., Pullman, WA (United States)
  5. Tsinghua Univ., Beijing (China)
+ Show Author Affiliations
The observation of the gaseous UFO– anion is reported, which is investigated using photoelectron spectroscopy and relativisitic ab initio calculations. Two strong photoelectron bands are observed at low binding energies due to electron detachment from the U-7sσ orbital. Numerous weak detachment bands are also observed due to the strongly correlated U-5f electrons. The electron affinity of UFO is measured to be 1.27(3) eV. High-level relativistic quantum chemical calculations have been carried out on the ground state and many low-lying excited states of UFO to help interpret the photoelectron spectra and understand the electronic structure of UFO. The ground state of UFO– is linear with an O–U–F structure and a 3H4 spectral term derived from a U 7sσ25fφ15fδ1 electron configuration, whereas the ground state of neutral UFO has a 4H7/2 spectral term with a U 7sσ15fφ15fδ1 electron configuration. Strong electron correlation effects are found in both the anionic and neutral electronic configurations. In the UFO neutral, a high density of electronic states with strong configuration mixing is observed in most of the scalar relativistic and spin-orbit coupled states. In conclusion, the strong electron correlation, state mixing, and spin-orbit coupling of the electronic states make the excited states of UFO very challenging for accurate quantum chemical calculations.
Research Organization:
Brown Univ., Providence, RI (United States)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
SC0006979; SC0008501
OSTI ID:
1469686
Alternate ID(s):
OSTI ID: 1239611
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 8 Vol. 144; ISSN JCPSA6; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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