Spin-dependent localized Hartree-Fock density-functional calculation of singly, doubly, and triply excited and Rydberg states of He- and Li-like ions

Journal Article · Tue Feb 01 04:00:00 EST 2005 · Physical Review. A

DOI:https://doi.org/10.1103/PhysRevA.71.022513· OSTI ID:20650080

Zhongyuan, Zhou ^[1]; Chu, Shih-I ^[1]

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1. Department of Chemistry, University of Kansas, Lawrence, Kansas 66045 (United States)

A spin-dependent density-functional approach for the calculation of highly and multiply excited state of atomic system is proposed based on the localized Hartree-Fock density-functional method and Slater's diagonal sum rule. In this approach, electron spin orbitals in an electronic configuration are obtained first by solving the Kohn-Sham equation with an exact nonvariational spin-dependent localized Hartree-Fock exchange potential. Then a single-Slater-determinant energy of the electronic configuration is calculated by using these electron spin orbitals. Finally, a multiplet energy of an excited state is evaluated from the single-Slater-determinant energies of the electronic configurations involved in terms of Slater's diagonal sum rule. This approach has been applied to the calculation of singly, doubly, and especially triply excited Rydberg states of He- and Li-like ions. The total energies obtained from the calculation with an exchange-only (X-only) potential are surprisingly close to those of Hartree-Fock method and the total energies from the calculation with exchange-correlation potential are in overall agreement with available theoretical and experimental data. The presented procedure provides a simple and computationally efficient scheme for the accurate calculation of highly and multiply excited Rydberg states of an atomic system within density-functional theory.

• OSTI ID: 20650080
• Journal Information: Physical Review. A, Journal Name: Physical Review. A Journal Issue: 2 Vol. 71; ISSN 1050-2947; ISSN PLRAAN
• Country of Publication: United States
• Language: English

Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
CATIONS
CORRELATIONS
DENSITY FUNCTIONAL METHOD
ELECTRONIC STRUCTURE
ELECTRONS
HARTREE-FOCK METHOD
POTENTIALS
RYDBERG STATES
SLATER METHOD
SPIN
SUM RULES
TRIPLETS