The generalized sturmian method for calculating spectra of atoms and ions
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The generalized sturmian method for calculating spectra of atoms and ions. / Avery, James Emil; Avery, John Scales.
In: Journal of Mathematical Chemistry, Vol. 33, 2003, p. 145-162.Research output: Contribution to journal › Journal article › Research › peer-review
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TY - JOUR
T1 - The generalized sturmian method for calculating spectra of atoms and ions
AU - Avery, James Emil
AU - Avery, John Scales
N1 - Paper id:: 10.1023/A:1023204016217
PY - 2003
Y1 - 2003
N2 - 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.
AB - 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.
KW - Faculty of Science
KW - Sturm-baser
KW - den generalisede Sturm-metode
KW - atomspektre
KW - kvantekemi
KW - Sturmian bases
KW - generalized Sturmian method
KW - atomic spectra
KW - quantum chemistry
U2 - 10.1023/A:1023204016217
DO - 10.1023/A:1023204016217
M3 - Journal article
VL - 33
SP - 145
EP - 162
JO - Journal of Mathematical Chemistry
JF - Journal of Mathematical Chemistry
SN - 0259-9791
ER -
ID: 124785