Universal Theoretical Approach to Extract Anisotropic Spin Hamiltonians
- 2 October 2009
- journal article
- Published by American Chemical Society (ACS) in Journal of Chemical Theory and Computation
- Vol. 5 (11), 2977-2984
- https://doi.org/10.1021/ct900326e
Abstract
International audienceMonometallic 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 parametersKeywords
This publication has 55 references indexed in Scilit:
- Calculation of the zero-field splitting tensor on the basis of hybrid density functional and Hartree-Fock theoryThe Journal of Chemical Physics, 2007
- First-principles calculations of zero-field splitting parametersThe Journal of Chemical Physics, 2006
- Importance of Direct Spin−Spin Coupling and Spin-Flip Excitations for the Zero-Field Splittings of Transition Metal Complexes: A Case StudyJournal of the American Chemical Society, 2006
- Molecular NanomagnetsPublished by Oxford University Press (OUP) ,2006
- Calculating the Electron Paramagnetic Resonance Parameters of Exchange Coupled Transition Metal Complexes Using Broken Symmetry Density Functional Theory: Application to a MnIII/MnIV Model CompoundJournal of the American Chemical Society, 2004
- Graphical Abstract: Angew. Chem. Int. Ed. 3/2003Angewandte Chemie-International Edition, 2003
- Calculation of Zero-Field Splittings, g-Values, and the Relativistic Nephelauxetic Effect in Transition Metal Complexes. Application to High-Spin Ferric ComplexesInorganic Chemistry, 1998
- Macroscopic quantum tunnelling of magnetization in a single crystal of nanomagnetsNature, 1996
- Macroscopic Measurement of Resonant Magnetization Tunneling in High-Spin MoleculesPhysical Review Letters, 1996
- Alternating current susceptibility, high field magnetization, and millimeter band EPR evidence for a ground S = 10 state in [Mn12O12(Ch3COO)16(H2O)4].2CH3COOH.4H2OJournal of the American Chemical Society, 1991