Abstract
A DV-Xα molecular-orbital calculation was carried out on [Ce(OH2)9]3+. The charge donation of coordinated water molecules results in a net charge of +0·354 on the central tervalent metal ion and an appreciable polarization in the coordinated waters. The coordination bond of the vertex waters is stronger than that of the equatorials. The observed transition moments and energies of the 5d ← 4f excitations as well as the observed ligand-field splitting of 2 D(5d 1) multiplet in the D 3h ligand field of [Ce(OH2)9]3+ were reasonably reproduced by use of the transition-state approximation on the base of DV-Xα molecular-orbital calculation. The model also predicts a contraction of 4f orbital while an expansion of 5d orbital in the cluster. The one-electron energies of 4f, 5d and 6s orbitals as well as the spin-orbit coupling energies in Ce3+ free ion were also calculated by the relativistic DV-Xα method. The relativistic equation reproduces the observed values only for α = 1·0 rather than the traditional value α = 0·7.
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