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

Borel, Alain; Helm, Lothar; Daul, Claude

doi:10.1016/j.cplett.2003.11.082

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Journal article

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

Borel, Alain Institut de Chimie Moléculaire et Biologique, Ecole Polytechnique Fédérale de Lausanne, Lausanne, Switzerland
Helm, Lothar Institut de Chimie Moléculaire et Biologique, Ecole Polytechnique Fédérale de Lausanne, Lausanne, Switzerland
Daul, Claude Inorganic Chemistry Department, University of Fribourg, Switzerland

13.12.2003

Published in:

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

English 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.

Faculty

Faculté des sciences et de médecine

Department

Département de Chimie

Language