Variational predictions of transition energies and electron affinities: He and Li ground states and Li, Be, and Mg core-excited states
- 1 April 1990
- journal article
- research article
- Published by American Physical Society (APS) in Physical Review A
- Vol. 41 (7) , 3481-3488
- https://doi.org/10.1103/physreva.41.3481
Abstract
Variational procedures for predicting energy differences of many-electron systems are investigated. Several different calculations for few-electron systems are considered that illustrate the problems encountered when a many-electron system is modeled as a core plus outer electrons. It is shown that sequences of increasingly more accurate calculations for outer correlation may converge yielding wrong transition energies. At the same time, accurate core-polarization calculations overestimate the binding energy, requiring a core-valence correction. For the high-spin, core-excited states of Li, it was found that outer correlation only predicted electron affinities as accurately as full-correlation studies. This observation suggested a prediction of the core-excited PS transition in , based on observed P transition energies of the neutral species, predicted electron affinities including only outer correlation, and a core-valence correction, that is shown to be in good agreement with experiment. A similar calculation for predicts a wavelength of 2895.1 Å for this transition.
Keywords
This publication has 27 references indexed in Scilit:
- GRASP: A general-purpose relativistic atomic structure programComputer Physics Communications, 1989
- Second-order energies and third-order matrix elements of alkali-metal atomsPhysical Review A, 1987
- Atomic Many-Body TheoryPublished by Springer Nature ,1986
- An iterative, numeric procedure to obtain pair functions applied to two-electron systemsJournal of Physics B: Atomic and Molecular Physics, 1979
- Piecewise polynomial configuration interaction natural orbital study of 1 s2 heliumThe Journal of Chemical Physics, 1979
- Numerical solution of general Hartree-Fock equations for atomsJournal of Computational Physics, 1978
- A multi-configuration Hartree-Fock programComputer Physics Communications, 1970
- Many-Electron Theory of Atoms and Molecules. IIThe Journal of Chemical Physics, 1962
- Many-Electron Theory of Atoms and Molecules. I. Shells, Electron Pairs vs Many-Electron CorrelationsThe Journal of Chemical Physics, 1962
- Ground State of Two-Electron AtomsPhysical Review B, 1958