Density-functional study of two Fe4-based single-molecule magnets -: art. no. 044303

We present the results of our all-electron density-functional calculations on the electronic structure and magnetic anisotropy energy of the [Fe-4(OMe)(6)(dpm)(6)] and [Fe-4(thme)(2)(dpm)(6)] molecular clusters, which are experimentally found to behave as single-molecule magnets. The calculated magnetic anisotropy energy barriers are 2.65 and 15.8 K, respectively, which agree with the experimental data. We also present a density-functional study on the effect of the structure distortions on the magnetic anisotropy of the [Fe(H2O)(6)](3+) complex. This study, together with an analysis of the projected anisotropies of each iron ion in both molecular clusters, allows us to qualitatively understand why the magnetic anisotropy energy (MAE) barrier of the second single-molecule magnet (SMM) is larger than the MAE of the first SMM. (C) 2005 American Institute of Physics.