The calculation of the ligand field energies of cobalt porphyrins from E.S.R. data
Titel:
The calculation of the ligand field energies of cobalt porphyrins from E.S.R. data
Auteur:
Lin, W. C.
Verschenen in:
Molecular physics
Paginering:
Jaargang 31 (1976) nr. 3 pagina's 657-662
Jaar:
1976-03
Inhoud:
Griffith's original equations were applied with modifications to the study of the E.S.R. of cobalt porphyrins. From the first-order equations for g⊥, A‖, and A⊥, the relative orbital energies of dx2 - y2(b1), dz2(a1), and dxz, dyz(e) could be calculated. The relative orbital energy of dxy(b2) calculated from the second-order equation for g‖ was always too high. This failure was attributed to the breakdown of the perturbation treatment due to the closeness of 2E, 4E and 4A2 excited states to the 2A1 ground state. The calculation of the g‖ value from assumed value of the energy of b2 led to the assignment of the signs of hyperfine coupling constants as A‖ > 0, A⊥ > 0 for uncoordinate cobalt porphyrins and A > 0, A < 0 for solvent coordinated complexes.
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