期刊
JOURNAL OF CHEMICAL PHYSICS
卷 133, 期 8, 页码 -出版社
AMER INST PHYSICS
DOI: 10.1063/1.3480014
关键词
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资金
- Spanish Ministry of Science and Innovation [CTQ2008-06644-C02-01]
- Generalitat de Catalunya [2009SGR462]
- French Centre National de la Recherche Scientifique (CNRS)
- Universite de Toulouse
- Agence Nationale de la Recherche (ANR) [ANR-09-BLAN-0195-01]
- Agence Nationale de la Recherche (ANR) [ANR-09-BLAN-0195] Funding Source: Agence Nationale de la Recherche (ANR)
- ICREA Funding Source: Custom
The zero-field splitting (ZFS) of a model monometallic Mn(III) complex is theoretically studied as function of a systematic symmetry lowering. First, we treat the octahedral case for which the standard S.D.S model Hamiltonian cannot be applied due to a zero-field splitting in the absence of anisotropy induced by the spin-orbit coupling between the two spatial components of the E-5(g) state at second-order of perturbation. Next, the symmetry is lowered to D-4h and D-2h and the anisotropic spin Hamiltonian is extracted using effective Hamiltonian theory. A simple relation is derived between the ratio E/vertical bar D vertical bar and the applied rhombic and axial distortions. Moreover, it is shown that close to O-h symmetry, the orbital mixing due to spin-orbit coupling can be accurately described with Stevens fourth-order operators. The calculated tendencies are interpreted within a refined Racah plus ligand field model and it is shown that the ZFS parameters in Mn(III) complexes follow special rules that are nonintuitive compared to other d(n) configurations. Finally, some angular distortions are applied to study their effect on the anisotropy. (C) 2010 American Institute of Physics. [doi: 10.1063/1.3480014]
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