Comments on Koopmans' theorem and electron relaxation with valence ionization

David C. Calabro, Dennis L Lichtenberger

Research output: Contribution to journalArticle

35 Citations (Scopus)

Abstract

The electron relaxation energy, ER, is a well-recognized limitation of Koopmans' approximation for ionization energies. Several characteristic aspects of ER for first ionizations of atoms are discussed. It is shown that (1) Slater's screening model gives good account of the basic trends in ER with valence ionizations of main-group atoms but fails for d electron ionizations of transition metals, (2) the relatively large ER for ionization of 3d electrons is association with the 3d shielding of 3s and 3p electrons (these relaxation characteristics help to clarify the filling of the 4s and 3d orbitals in the periodic table), and (3) there is more than a proportional decrease in ER when the valence density removed from an atom is less than a complete electron (this indicates that the intraatomic portion of ER will be less for ionization from a delocalized orbital than from a localized orbital).

Original languageEnglish (US)
Pages (from-to)1732-1734
Number of pages3
JournalInorganic Chemistry
Volume19
Issue number6
StatePublished - 1980

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Ionization
theorems
valence
ionization
Electrons
electrons
Atoms
orbitals
Ionization potential
atoms
Shielding
Transition metals
Screening
shielding
Association reactions
screening
transition metals
trends
energy
approximation

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Comments on Koopmans' theorem and electron relaxation with valence ionization. / Calabro, David C.; Lichtenberger, Dennis L.

In: Inorganic Chemistry, Vol. 19, No. 6, 1980, p. 1732-1734.

Research output: Contribution to journalArticle

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