Atanasov, Mihail Daul, Claude Rohmer, Marie-Madeleine Venkatachalam, Tamilmani 2006-07-06 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 <i>g</i>-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 <i>g</i>-values is too small. Using a numerical adjustment of nuclear charge for Cu, a good agreement between the computed and the experimental <i>g</i>-tensor values is observed. The influence of the DFT functional on the calculated <i>g</i>-tensor is also discussed. application/pdf https://folia.unifr.ch/global/documents/300253 https://folia.unifr.ch/documents/300253/files/daul_dbl.pdf eng info:eu-repo/semantics/altIdentifier/doi/10.1016/j.cplett.2006.06.107 info:eu-repo/semantics/openAccess License undefined Chemical Physics Letters. - 2006, vol. 427, no. 4-6, p. 449-454 info:eu-repo/classification/udc/54 A DFT based ligand field study of the EPR spectra of Co(II) and Cu(II) porphyrins http://purl.org/coar/resource_type/c_6501