Experimental and theoretical studies of vibrational density of states in Fe3O4 single-crystalline thin films

This paper presents experimental and theoretical studies of lattice vibrations in a single-crystalline Fe3O4(001) thin film. The investigations were carried out in order to see how the lattice dynamics changes at the Verwey transition. Vibrational densities of states (DOS) were obtained from nuclear inelastic scattering (NIS) of synchrotron radiation in the temperature range 25 to 296 K, while theoretical DOS were calculated ab initio within density functional theory. Experimental phonon density of states shows good agreement with calculated DOS, reproducing both the general features of main line groups as well as the groups' structure. This is also in qualitative accord with heat capacity data, provided that experimental DOS is augmented with that calculated for oxygen atoms. We have observed a gradual change in the NIS raw data as well as the relevant DOS while lowering the temperature. In particular, the main peak in the energy region 15-25 meV shows increasing splitting on cooling. The Lamb-Mossbauer factor calculated in the course of DOS evaluation shows a pronounced drop in the vicinity of the Verwey transition that may be partly connected to the observed abrupt lowering of the count rate at approximately 7 meV for T <T-V. Since this is an indication of lattice stiffening below T-V, we conclude that we have found experimental evidence for lattice participation in the mechanism leading to the Verwey transition.