ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
A zero-free-parameter ligand field model is used to account for the observed low-lying (E〈10 000 cm−1) electronic states of LaF. The electronic structure of LaF is represented as the effect of a nonpolarizable point F− ligand on the two valence electrons of a free La+ atomic ion. Free-ion configuration interaction (CI) effects (represented by a parametric fit of the free La+ energy levels to Fk,Gk Slater–Condon electrostatic and ζ spin–orbit parameters) and ligand-driven CI (treated by Bk0 ligand field radial integrals evaluated using Hartree–Fock La+ orbitals) are included in the model. A series of calculations is described, from the simplest "primitive LFT model'' which includes the three lowest-lying and most important configurations (6s2, 5d6s, 5d2) to the most elaborate "balanced s-polarized LFT model'' which includes six configurations (6s2, 5d6s, 5d2, 6s6p, 5d6p, and 6p2) in order to account properly for s–p polarization effects. The inclusion of ligand-driven CI (metal-centered orbital polarization) effects shows that simple electrostatic atomic-ion-in-molecule models are capable of accounting for the electronic structure of many highly polar diatomic molecules having more than a single metal-centered valence electron.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.453078
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