Electronic spectra of DyF studied by four-component relativistic configuration interaction methods

Journal Article · Sat Mar 07 04:00:00 EST 2015 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4913631· OSTI ID:22416224

Yamamoto, Shigeyoshi ^[1]; Tatewaki, Hiroshi ^[2]

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1. School of International Liberal Studies, Chukyo University, 101-2 Yagoto-Honmachi, Showa-ku, Nagoya 466-8666 (Japan)
2. Institute of Advanced Studies in Artificial Intelligence, Chukyo University, Toyota 470-0393 (Japan)

The electronic states of the DyF molecule below 3.0 eV are studied using 4-component relativistic CI methods. Spinors generated by the average-of-configuration Hartree-Fock method with the Dirac-Coulomb Hamiltonian were used in CI calculations by the KRCI (Kramers-restricted configuration interaction) program. The CI reference space was generated by distributing 11 electrons among the 11 Kramers pairs composed mainly of Dy [4f], [6s], [6p] atomic spinors, and double excitations are allowed from this space to the virtual molecular spinors. The CI calculations indicate that the ground state has the dominant configuration (4f{sup 9})(6s{sup 2})(Ω = 7.5). Above this ground state, 4 low-lying excited states (Ω = 8.5, 7.5, 7.5, 7.5) are found with dominant configurations (4f{sup 10})(6s). These results are consistent with the experimental studies of McCarthy et al. Above these 5 states, 2 states were observed at T{sub 0} = 2.39 eV, 2.52 eV by McCarthy et al. and were named as [19.3]8.5 and [20.3]8.5. McCarthy et al. proposed that both states have dominant configurations (4f{sup 9})(6s)(6p), but these configurations are not consistent with the large R{sub e}’s (∼3.9 a.u.) estimated from the observed rotational constants. The present CI calculations provide near-degenerate states of (4f{sup 10})(6p{sub 3/2,1/2}), (4f{sup 10})(6p{sub 3/2,3/2}), and (4f{sup 9})(6s)(6p{sub 3/2,1/2}) at around 3 eV. The former two states have larger R{sub e} (3.88 a.u.) than the third, so that it is reasonable to assign (4f{sup 10})(6p{sub 3/2,1/2}) to [19.3]8.5 and (4f{sup 10})(6p{sub 3/2,3/2}) to [20.3]8.5.

• OSTI ID: 22416224
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 9 Vol. 142; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
74 ATOMIC AND MOLECULAR PHYSICS
CONFIGURATION INTERACTION
DYSPROSIUM FLUORIDES
ELECTRON SPECTRA
ELECTRONS
EV RANGE
EXCITATION
EXCITED STATES
GROUND STATES
HAMILTONIANS
HARTREE-FOCK METHOD
MOLECULES
RELATIVISTIC RANGE
SPINORS