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Valence shell excitation accompanying photoionization in mercury

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.1682379· OSTI ID:1169919
 [1];  [1];  [1];  [2]
  1. Argonne National Laboratory (ANL), Argonne, IL (United States)
  2. Insitut Max von Laue-Paul Langevin, Grenoble (France)
The 584 Å photoelectron spectrum of mercury vapor exhibits weak peaks corresponding to formation of the excited (5d)¹⁰ (6p) ²P 1/2,3/2 ionic states, in addition to the one-electron transitions, which produce the (5d)¹⁰ (6s)² S1/2 and (5d)⁹ (6s)² ²D 5/2,3/2 states of Hg+. Although the ²P 1/2,3/2 states are forbidden by the usual shakeup mechanism, they can occur either by a "conjugate" shakeup process or by configuration interaction (CI) in the initial state. We present calculations which indicate that the latter is responsible for ~80% of the ²P 1/2,3/2 intensity observed. The 304 Å photoelectron spectrum provides evidence for formation of additional excited ionic states which may have the configuration (5d)⁹ (6p)² and/or (5d)⁹ 6s 7s. Our calculations show that the energies of these states are in the region of peaks experimentally observed. The (5d)⁹ (6p)² states can be formed by the initial-state CI mechanism, whereas the (5d)⁹ 6s 7s states are attainable via the shakeup process. The probabilities for these two transitions are comparable.
Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
US Atomic Energy Commission (AEC)
DOE Contract Number:
W-31109-ENG-38
OSTI ID:
1169919
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 7 Vol. 61; ISSN JCPSA6; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English

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