Faculté des sciences

Hybrid ligand-field theory/quantum chemical calculation of the fine structure and ZFS in lanthanide(III) complexes

Borel, Alain ; Helm, Lothar ; Daul, Claude A.

In: Chemical Physics Letters, 2004, vol. 383 (5-6), p. 584-591

Ligand field effects in lanthanide ions compounds have consequences for optical and magnetic spectroscopy. In the analysis of electron paramagnetic resonance spectra of Gd³⁺ complexes, a major role is played by the zero field splitting (ZFS), which is a high order consequence of the ligand field and the spin–orbit coupling. We present a general parameterized method and a computer program for... More

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    Summary
    Ligand field effects in lanthanide ions compounds have consequences for optical and magnetic spectroscopy. In the analysis of electron paramagnetic resonance spectra of Gd³⁺ complexes, a major role is played by the zero field splitting (ZFS), which is a high order consequence of the ligand field and the spin–orbit coupling. We present a general parameterized method and a computer program for the study of the excited states of lanthanide complexes. We apply it for the first principles determination of the ZFS of the [Gd(H₂O)₈]³⁺ aqua ion and the corresponding EPR peak-to-peak width in solution. We calculate the influence of the various contributions to the effective Hamiltonian on the splitting of the ground state multiplet.