Calculating the Electron Paramagnetic Resonance Parameters of Exchange Coupled Transition Metal Complexes Using Broken Symmetry Density Functional Theory: Application to a MnIII/MnIV Model Compound

摘要: The capability of the density functional broken symmetry approach for calculation various EPR parameters exchange coupled metal clusters is demonstrated by studying experimentally well-investigated [MnIIIMnIV(μ-O)2(μ-OAc)DTNE]2+ complex. Geometry optimizations complex in its and high spin states yielded structures with two distinct manganese sites geometrical good agreement X-ray structure. Exchange coupling constants were calculated from energy differences between using Heisenberg Hamiltonian. Very theory experiment was achieved B3LYP hybrid functional. g-tensor calculations performed employing perturbed Kohn−Sham equations. A strategy computation site values presented provides single-site g-tensors that are expectations MnIII MnIV, respectively. Spin projection gave ...