A DFT based ligand field study of the EPR spectra of Co(II) and Cu(II) porphyrins
- Atanasov, Mihail Département de Chimie de l’Université de Fribourg, Switzerland - Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, Sofia, Bulgaria
- Daul, Claude Département de Chimie de l’Université de Fribourg, Switzerland
- Rohmer, Marie-Madeleine Laboratoire de Chimie Quantique, Strasbourg, France
- Venkatachalam, Tamilmani Département de Chimie de l’Université de Fribourg, Switzerland
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06.07.2006
Published in:
- Chemical Physics Letters. - 2006, vol. 427, no. 4-6, p. 449-454
English
Using a DFT based Ligand Field treatment (LFDFT) of the electronic structure of Co(II) and Cu(II) porphyrins (CoP and CuP) we analyse the origin of their EPR spectra. From a comparison between theoretical result on Co model clusters (CoP and CoP–ZnP dimer) we conclude that the g-tensor values are very sensitive to the axial coordination which stabilizes a ²A₁ ground state in good agreement with experimental data. In contrast, DFT overestimates Cu–ligand covalency, leading to large discrepancy with experiments, and hence the orbital contribution to the computed g-values is too small. Using a numerical adjustment of nuclear charge for Cu, a good agreement between the computed and the experimental g-tensor values is observed. The influence of the DFT functional on the calculated g-tensor is also discussed.
- Faculty
- Faculté des sciences et de médecine
- Department
- Département de Chimie
- Language
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- English
- Classification
- Chemistry
- License
- License undefined
- Identifiers
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- RERO DOC 6328
- DOI 10.1016/j.cplett.2006.06.107
- Persistent URL
- https://folia.unifr.ch/unifr/documents/300253
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