22 research outputs found
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 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) 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, FeO, 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 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
and 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 and Hund's exchange . 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 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
(FeO) 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