Strong Effects of Cation Vacancies on the Electronic and Dynamical Properties of FeO

We report pronounced modifications of electronic and vibrational properties induced in FeO by cation vacancies, obtained within density functional theory incorporating strong local Coulomb interactions at Fe atoms. The insulating gap of FeO is reduced by about 50% due to unoccupied electronic bands introduced by trivalent Fe ions stabilized by cation vacancies. The changes in the electronic structure along with atomic displacements induced by cation vacancies affect strongly phonon dispersions via modified force constants, including those at atoms beyond nearest neighbors of defects. We demonstrate that theoretical phonon dispersions and their densities of states reproduce the results of inelastic neutron and nuclear resonant x-ray scattering experiments \emph{only} when Fe vacancies and Coulomb interaction $U$ are both included explicitly in \emph{ab initio} simulations, which also suggests that the electron-phonon coupling in FeO is strong.Comment: 5 pages, 4 figure

Anharmonicity due to Electron-Phonon Coupling in Magnetite

We present the results of inelastic x-ray scattering for magnetite and analyze the energies and spectral widths of the phonon modes with different symmetries in a broad range of temperature 125<T<293 K. The phonon modes with X_4 and Delta_5 symmetries broaden in a nonlinear way with decreasing temperature when the Verwey transition is approached. It is found that the maxima of phonon widths occur away from high-symmetry points which indicates the incommensurate character of critical fluctuations. Strong phonon anharmonicity induced by electron-phonon coupling is discovered within ab initio calculations which take into account local Coulomb interactions at Fe ions. It (i) explains observed anomalous phonon broadening, and (ii) demonstrates that the Verwey transition is a cooperative phenomenon which involves a wide spectrum of phonons coupled to charge fluctuations condensing in the low-symmetry phase.Comment: 5 pages, 5 figures, accepted in Physical Review Letter

Structure and elastic properties of Mg(OH)2_2 from density functional theory

The structure, lattice dynamics and mechanical properties of the magnesium hydroxide have been investigated with static density functional theory calculations as well as \it {ab initio} molecular dynamics. The hypothesis of a superstructure existing in the lattice formed by the hydrogen atoms has been tested. The elastic constants of the material have been calculated with static deformations approach and are in fair agreement with the experimental data. The hydrogen subsystem structure exhibits signs of disordered behaviour while maintaining correlations between angular positions of neighbouring atoms. We establish that the essential angular correlations between hydrogen positions are maintained to the temperature of at least 150 K and show that they are well described by a physically motivated probabilistic model. The rotational degree of freedom appears to be decoupled from the lattice directions above 30K

Short-Range Correlations in Magnetite above the Verwey Temperature

Magnetite, Fe$_3$O$_4$, is the first magnetic material discovered and utilized by mankind in Ancient Greece, yet it still attracts attention due to its puzzling properties. This is largely due to the quest for a full and coherent understanding of the Verwey transition that occurs at $T_V=124$ K and is associated with a drop of electric conductivity and a complex structural phase transition. A recent detailed analysis of the structure, based on single crystal diffraction, suggests that the electron localization pattern contains linear three-Fe-site units, the so-called trimerons. Here we show that whatever the electron localization pattern is, it partially survives up to room temperature as short-range correlations in the high-temperature cubic phase, easily discernible by diffuse scattering. Additionally, {\it ab initio} electronic structure calculations reveal that characteristic features in these diffuse scattering patterns can be correlated with the Fermi surface topology.Comment: 7 pages, 6 figure

Origin of the Verwey transition in magnetite: Group theory, electronic structure, and lattice dynamics study

The Verwey phase transition in magnetite has been analyzed using the group theory methods. It is found that two order parameters with the symmetries $X_3$ and $\Delta_5$ induce the structural transformation from the high-temperature cubic to the low-temperature monoclinic phase. The coupling between the order parameters is described by the Landau free energy functional. The electronic and crystal structure for the cubic and monoclinic phases were optimized using the {\it ab initio} density functional method. The electronic structure calculations were performed within the generalized gradient approximation including the on-site interactions between 3d electrons at iron ions -- the Coulomb element $U$ and Hund's exchange $J$. Only when these local interactions are taken into account, the phonon dispersion curves, obtained by the direct method for the cubic phase, reproduce the experimental data. It is shown that the interplay of local electron interations and the coupling to the lattice drives the phonon order parameters and is responsible for the opening of the gap at the Fermi energy. Thus, it is found that the metal-insulator transition in magnetite is promoted by local electron interactions, which significantly amplify the electron-phonon interaction and stabilize weak charge order coexisting with orbital order of the occupied $t_{2g}$ states at Fe ions. This provides a scenario to understand the fundamental problem of the origin of the Verwey transition in magnetite.Comment: 17 pages, 5 figures, 8 tables. Accepted version to be published in Phys. Rev.

Coherent generation of symmetry-forbidden phonons by light-induced electron-phonon interactions in magnetite

Symmetry breaking across phase transitions often causes changes in selection rules and emergence of optical modes which can be detected via spectroscopic techniques or generated coherently in pump-probe experiments. In second-order or weakly first-order transitions, fluctuations of the order parameter are present above the ordering temperature, giving rise to intriguing precursor phenomena, such as critical opalescence. Here, we demonstrate that in magnetite (Fe$_3$O$_4$) light excitation couples to the critical fluctuations of the charge order and coherently generates structural modes of the ordered phase above the critical temperature of the Verwey transition. Our findings are obtained by detecting coherent oscillations of the optical constants through ultrafast broadband spectroscopy and analyzing their dependence on temperature. To unveil the coupling between the structural modes and the electronic excitations, at the origin of the Verwey transition, we combine our results from pump-probe experiments with spontaneous Raman scattering data and theoretical calculations of both the phonon dispersion curves and the optical constants. Our methodology represents an effective tool to study the real-time dynamics of critical fluctuations across phase transitions

Phonon confinement and spin-phonon coupling in tensile-strained ultrathin EuO films

Reducing the material sizes to the nanometer length scale leads to drastic modifications of the propagating lattice excitations (phonons) and their interactions with electrons and magnons. In EuO, a promising material for spintronic applications in which a giant spin-phonon interaction is present, this might imply a reduction of the degree of spin polarization in thin films. Therefore, a comprehensive investigation of the lattice dynamics and spin-phonon interaction in EuO films is necessary for practical applications. We report a systematic lattice dynamics study of ultrathin EuO(001) films using nuclear inelastic scattering on the Mössbauer-active isotope ^{151}Eu and first-principles theory. The films were epitaxially grown on YAlO_{3}(110), which induces a tensile strain of ca. 2%. By reducing the EuO layer thickness from 8 nm to a sub-monolayer coverage, the Eu-partial phonon density of states (PDOS) reveals a gradual enhancement of the number of low-energy phonon states and simultaneous broadening and suppression of the peaks. These deviations from bulk features lead to significant anomalies in the vibrational thermodynamic and elastic properties calculated from the PDOS. The experimental results, supported by first-principles theory, unveil a reduction of the strength of the spin-phonon interaction in the tensile-strained EuO by a factor of four compared to a strain-free lattice