The generalized sturmian method for calculating spectra of atoms and ions

Research output: Contribution to journalJournal articleResearchpeer-review

James Emil Avery, John Scales 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.
Original languageEnglish
JournalJournal of Mathematical Chemistry
Volume33
Pages (from-to)145-162
ISSN0259-9791
DOIs
Publication statusPublished - 2003

    Research areas

  • Faculty of Science - Sturmian bases, generalized Sturmian method, atomic spectra, quantum chemistry

ID: 124785