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Updated: Apr 18, 2026
Spatial Separation of Molecular Conformers and Clusters
Published on: January 9, 2014
Systematic theoretical investigation of the zero-field splitting in Gd(III) complexes: wave function and density
Shehryar Khan1, Aleksandra Kubica-Misztal2, Danuta Kruk3
1Department of Physics, Stockholm University, AlbaNova University Center, S-106 91 Stockholm, Sweden.
Abstract:
The zero-field splitting (ZFS) of the electronic ground state in paramagnetic ions is a sensitive probe of the variations in the electronic and molecular structure with an impact on fields ranging from fundamental physical chemistry to medical applications. A detailed analysis of the ZFS in a series of symmetric Gd(III) complexes is presented in order to establish the applicability and accuracy of computational methods using multiconfigurational complete-active-space self-consistent field wave functions and of density functional theory calculations. The various computational schemes are then applied to larger complexes Gd(III)DOTA(H2O)(-), Gd(III)DTPA(H2O)(2-), and Gd(III)(H2O)8(3+) in order to analyze how the theoretical results compare to experimentally derived parameters. In contrast to approximations based on density functional theory, the multiconfigurational methods produce results for the ZFS of Gd(III) complexes on the correct order of magnitude.
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