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Double breakdown of Koopmans' theorem and strong correlation satellites in the He II photoelectron spectrum of O3

Authors
Journal
Chemical Physics
0301-0104
Publisher
Elsevier
Publication Date
Volume
58
Issue
2
Identifiers
DOI: 10.1016/0301-0104(81)80062-6
Disciplines
  • Mathematics

Abstract

Abstract Because of the biradical nature of the ground state-of O 3 and the presence of some lone-pair orbitals, it is necessary to take into account both th initial-state and final-ionic-state configuration interaction (ISCI and FISCI) effects in analyzing the photoelectron spectrum (PES) of O 3. The disagreement concerning both experimental and theoretical assignments of the second and third states of O 3 + is resolved by performing nearly full-valence CI calculations with the minimal basis set. The third ionized state is identified with the zA 2 state which is described mainly by the ionization from the highest occupied molecular orbital 1a z; Koopmans' theorem is doubly broken. In addition, the complicated structures observed below 22 eV in the He II PES are discussed in terms of ISCI and FISCI.

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