Journal of Mathematical Chemistry

, Volume 33, Issue 2, pp 145–162 | Cite as

The Generalized Sturmian Method for Calculating Spectra of Atoms and Ions

  • James Avery
  • John Avery


The properties of generalized Sturmian basis sets are reviewed, and functions of this type are used to perform direct configuration interaction calculations on the spectra of atoms and ions. Singlet excited states calculated in this way show good agreement with experimentally measured spectra. When the generalized Sturmian method is applied to atoms, the configurations are constructed from hydrogenlike atomic orbitals with an effective charge which is characteristic of the configuration. Thus, orthonormality between the orbitals of different configurations cannot be assumed, and the generalized Slater–Condon rules must be used. This aspect of the problem is discussed in detail. Finally spectra are calculated in the presence of a strong external electric field. In addition to the expected Stark effect, the calculated spectra exhibit anomalous states. These are shown to be states where one of the electrons is primarily outside the atom or ion, with only a small amplitude inside.


Physical Chemistry Small Amplitude External Electric Field Effective Charge Atomic Orbital 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.


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Copyright information

© Plenum Publishing Corporation 2003

Authors and Affiliations

  • James Avery
    • 1
  • John Avery
    • 2
  1. 1.Institute of Computer ScienceUniversity of CopenhagenCopenhagenDenmark
  2. 2.H.C. Ørsted InstituteUniversity of CopenhagenCopenhagenDenmark

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