Universal Theoretical Approach to Extract Anisotropic Spin Hamiltonians

• Published in: Journal of chemical theory and computation Vol. 5; no. 11; pp. 2977 - 2984
• Main Authors: Maurice, Rémi, Bastardis, Roland, Graaf, Coen de, Suaud, Nicolas, Mallah, Talal, Guihéry, Nathalie
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 10.11.2009
• Subjects: Quantum Electronic Structure
• ISSN: 1549-9618; 1549-9626
• DOI: 10.1021/ct900326e

Monometallic Ni(II) and Co(II) complexes with large magnetic anisotropy are studied using correlated wave function based ab initio calculations. Based on the effective Hamiltonian theory, we propose a scheme to extract both the parameters of the zero-field splitting (ZFS) tensor and the magnetic anisotropy axes. Contrarily to the usual theoretical procedure of extraction, the method presented here determines the sign and the magnitude of the ZFS parameters in any circumstances. While the energy levels provide enough information to extract the ZFS parameters in Ni(II) complexes, additional information contained in the wave functions must be used to extract the ZFS parameters of Co(II) complexes. The effective Hamiltonian procedure also enables us to confirm the validity of the standard model Hamiltonian to produce the magnetic anisotropy of monometallic complexes. The calculated ZFS parameters are in good agreement with high-field, high-frequency electron paramagnetic resonance spectroscopy and frequency domain magnetic resonance spectroscopy data. A methodological analysis of the results shows that the ligand-to-metal charge transfer configurations must be introduced in the reference space to obtain quantitative agreement with the experimental estimates of the ZFS parameters.