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

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 3H 4 spectral term derived from a U 7sσ 25fφ 15fδ 1 electron configuration, whereas the ground state of neutral UFO has a 4H 7/2 spectral term with a U 7sσ 15fφ 15fδ 1 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 themore » electronic states make the excited states of UFO very challenging for accurate quantum chemical calculations.« less
Authors:
 [1] ;  [2] ; ORCiD logo [2] ; ORCiD logo [2] ;  [3] ; ORCiD logo [4] ; ORCiD logo [4] ;  [2] ; ORCiD logo [1]
  1. Tsinghua Univ., Beijing (China)
  2. Brown Univ., Providence, RI (United States)
  3. Chinese Academy of Sciences, Shanghai (China)
  4. Washington State Univ., Pullman, WA (United States)
Publication Date:
Grant/Contract Number:
SC0006979; FG02-12ER16329
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 144; Journal Issue: 8; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
Brown Univ., Providence, RI (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS
OSTI Identifier:
1469686
Alternate Identifier(s):
OSTI ID: 1239611

Roy, Soumendra K., Jian, Tian, Lopez, Gary V., Li, Wei -Li, Su, Jing, Bross, David H., Peterson, Kirk A., Wang, Lai -Sheng, and Li, Jun. A combined photoelectron spectroscopy and relativistic ab initio studies of the electronic structures of UFO and UFO–. United States: N. p., Web. doi:10.1063/1.4942188.
Roy, Soumendra K., Jian, Tian, Lopez, Gary V., Li, Wei -Li, Su, Jing, Bross, David H., Peterson, Kirk A., Wang, Lai -Sheng, & Li, Jun. A combined photoelectron spectroscopy and relativistic ab initio studies of the electronic structures of UFO and UFO–. United States. doi:10.1063/1.4942188.
Roy, Soumendra K., Jian, Tian, Lopez, Gary V., Li, Wei -Li, Su, Jing, Bross, David H., Peterson, Kirk A., Wang, Lai -Sheng, and Li, Jun. 2016. "A combined photoelectron spectroscopy and relativistic ab initio studies of the electronic structures of UFO and UFO–". United States. doi:10.1063/1.4942188. https://www.osti.gov/servlets/purl/1469686.
@article{osti_1469686,
title = {A combined photoelectron spectroscopy and relativistic ab initio studies of the electronic structures of UFO and UFO–},
author = {Roy, Soumendra K. and Jian, Tian and Lopez, Gary V. and Li, Wei -Li and Su, Jing and Bross, David H. and Peterson, Kirk A. and Wang, Lai -Sheng and Li, Jun},
abstractNote = {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.},
doi = {10.1063/1.4942188},
journal = {Journal of Chemical Physics},
number = 8,
volume = 144,
place = {United States},
year = {2016},
month = {2}
}