On Spin Hamiltonian Fits to Mössbauer Spectra of High-Spin Fe(II) Porphyrinate Systems.

Fits to Mössbauer spectra of high-spin iron(II) porphyrinates have been applied to the Fe(II) model compounds octaethylporphyrin(1,2-dimethylimidazole) and tetra-paramethoxyporphyrin(1,2-dimethylimidazole). Mössbauer spectra have been measured on these compounds at 4.2 K in large applied fields. Spin Hamiltonians were used for fitting both the electronic and nuclear interactions. The fits are done by adjusting the Hamiltonian parameters to simultaneously minimize the total χ(2) for three different applied fields. In order to get best fits, the EFG tensor need to be rotated relative to the ZFS tensor. A comparative sensitivity analysis of their Spin Hamiltonian parameters has also been done on the ZFS parameters D, and the EFG asymmetry parameter η. The best fits suggest that both systems definitely have a negative quadrupole splitting, and that largest EFG component is tilted far from the z-axis of the ZFS tensor, which is likely to be near the heme normal.