Mixed configuration ground state in Iron(II) Phthalocyanine

Abstract: We calculate the angular dependence of the x-ray linear and circular dichroism at the $L_{2,3}$ edges of $\alpha$-Fe(II) Phthalocyanine (FePc) thin films using a ligand field model with full configuration interaction. We find the best agreement with the experimental spectra for a mixed ground state of $^3E_{g}(a_{1g}^2e_g^3b_{2g}^1)$ and $^3B_{2g}(a_{1g}^1e_g^4b_{2g}^1)$ with the two configurations coupled by the spin-orbit interaction. The $^3E_{g}(b)$ and $^3B_{2g}$ states have an easy axis and plane anisotropies, respectively. Our model accounts for an easy-plane magnetic anisotropy and the measured magnitudes of the in-plane orbital and spin moments. The proximity in energy of the two configurations allows a switching of the magnetic anisotropy from easy plane to easy axis with a small change in the crystal field, as recently observed for FePc adsorbed on an oxidized Cu surface. We also discuss the possibility of a quintet ground state ($^5A_{1g}$ is 250~meV above the ground state) with planar anisotropy by manipulation of the Fe-C bond length by depositing the complex on a substrate that is subjected to a mechanical strain.