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Qualitative propagator theory of AX4 Auger spectra

J. Chem. Phys. 81, 5873 (1984); doi:10.1063/1.447588

Issue Date: 20 December 1984

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J. V. Ortiz
Department of Chemistry, University of New Mexico, Albuquerque, New Mexico 87131
Nonempirical, parametrized two-electron propagator theory is employed in the characterization of molecular Auger spectra. Based on the Mulliken approximation for many-center Coulomb integrals, the model Hamiltonian requires three parameters for each valence atomic orbital: an exponent for a Slater function, an orbital energy, and an electron–electron repulsion integral. All of these quantities are taken from atomic calculations. Two-electron propagators are derived using the superoperator formalism. The working equations yield some popular expressions that have been used in interpreting molecular Auger spectra as special cases. Partitioning technique reveals qualitative factors that govern configuration mixing in the final state. Electron interaction can play a qualitatively dominant role in some of the final states. Some final states display localization of the holes on the same halogen atom, while others place holes on adjacent halogen atoms. This effect is especially pronounced for valence s orbital holes, but it is also observed for A-X bond orbitals and X lone pair orbitals. Trends in electronegativity differences and orbital sizes determine how much final state localization occurs. Propgator theory permits intensity borrowing between configurations leading to richer predicted spectra for the carbon Auger. The importance of using a theory that qualitatively supersedes molecular orbital theory is emphasized. The Journal of Chemical Physics is copyrighted by The American Institute of Physics.
History: Received 9 July 1984; accepted 14 August 1984
Permalink: http://link.aip.org/link/?JCPSA6/81/5873/1
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KEYWORDS and PACS

Keywords
PACS
  • 32.80.Hd
    Atomic spectra and interactions with photons Photon interactions with atoms Auger effect and inner-shell ionization
  • 33.80.-b
    Molecular spectra and interactions of molecules with photons Photon interactions with molecules
  • 33.60.-q
    Molecular spectra and interactions of molecules with photons Photoelectron spectra
  • YEAR: 1984

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
Publisher:
AIP is a member of CrossRef AIP

REFERENCES (27)
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