Geometric, electronic and magnetic structure of Fe$_{x}$O$_{y}^{+}$ clusters

Abstract

Correlation between geometry, electronic structure and magnetism of solids is both intriguing and elusive. This is particularly strongly manifested in small clusters, where a vast number of unusual structures appear. Here, we employ density functional theory in combination with a genetic search algorithm, GGA$+U$ and a hybrid functional to determine the structure of gas phase Fe$_{x}$O$_{y}^{+/0}$ clusters. For Fe$_{x}$O$_{y}$ cation clusters we also calculate the corresponding vibration spectra and compare them with experiments. We successfully identify Fe$_{3}$O$_{4}^{+}$, Fe$_{4}$O$_{5}^{+}$, Fe$_{4}$O$_{6}^{+}$, Fe$_{5}$O$_{7}^{+}$ and propose structures for Fe$_{6}$O$_{8}^{+}$. Within the triangular geometric structure of Fe$_{3}$O$_{4}^{+}$ a non-collinear, ferrimagnetic and ferromagnetic state are comparable in energy. Fe$_{4}$O$_{5}^{+}$ and Fe$_{4}$O$_{6}^{+}$ are ferrimagnetic with a residual magnetic moment of 1~\muB{} due to ionization. Fe$_{5}$O$_{7}^{+}$ is ferrimagnetic due to the odd number of Fe atoms. We compare the electronic structure with bulk magnetite and find Fe$_{4}$O$_{5}^{+}$, Fe$_{4}$O$_{6}^{+}$, Fe$_{6}$O$_{8}^{+}$ to be mixed valence clusters. In contrast, in Fe$_{3}$O$_{4}^{+}$ and Fe$_{5}$O$_{7}^{+}$ all Fe are found to be trivalent.