Journal article

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
Show more…
    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
  • English
Classification
Chemistry
License
License undefined
Identifiers
Persistent URL
https://folia.unifr.ch/unifr/documents/300253
Statistics

Document views: 22 File downloads:
  • daul_dbl.pdf: 3