title: Toward the control of the magnetic anisotropy of Fe(II) cubes: a DFT study.
abstract: We present the results of our all-electron density-functional calculations on the magnetic anisotropy of the [Fe4(sap)4(MeOH)4] and [Fe4(sae)4(MeOH)4] polynuclear complexes. Our calculations, which predict that only the second complex is a single-molecule magnet (with a magnetic anisotropy energy barrier of 5.6 K), are in qualitative agreement with the experimental data. The analysis of the projected anisotropies of each Fe(II) ion, together with a study of the variation of the D value as a function of several geometrical parameters, allows us to qualitatively understand the different magnetic behaviors of both complexes. In addition to this, we also present a simple rule based on the analysis of the molecular orbitals of the system that allows us to predict how to enhance (by a factor of 6, approximately) the magnetic anisotropy barrier of these systems. Specifically, we will show that, for high-spin Fe(II) ions, the local easy axis of magnetization is perpendicular to the plane defined by the Fe(II)-d orbital which is doubly occupied. If similar rules were found for other metal ions, rational synthetic strategies to control magnetic anisotropy could be established.
authors.affiliation: Departament de Química Física, Facultat de Química i Centre Especial de Recerca en Química Teórica, Parc Científic, Universitat de Barcelona, Av. Diagonal 647, Barcelona 08028, Spain. jribasjr@yahoo.es
authors.forename: Jordi
authors.initials: J
authors.lastname: Ribas-Arino
authors.forename: Tunna
authors.initials: T
authors.lastname: Baruah
authors.forename: Mark R
authors.initials: MR
authors.lastname: Pederson