318 research outputs found
Berry-phase treatment of the homogeneous electric field perturbation in insulators
A perturbation theory of the static response of insulating crystals to
homogeneous electric fields, that combines the modern theory of polarization
(MTP) with the variation-perturbation framework is developed, at unrestricted
order of perturbation. First, we address conceptual issues related to the
definition of such a perturbative approach. In particular, in our definition of
an electric-field-dependent energy functional for periodic systems, the
position operator appearing in the perturbation term is replaced by a
Berry-phase expression, along the lines of the MTP. Moreover, due to the
unbound nature of the perturbation, a regularization of the Berry-phase
expression for the polarization is needed in order to define a
numerically-stable variational procedure. Regularization is achieved by means
of discretization, which can be performed either before or after the
perturbation expansion. We compare the two possibilities and apply them to a
model tight-binding Hamiltonian. Lowest-order as well as generic formulas are
presented for the derivatives of the total energy, the normalization condition,
the eigenequation, and the Lagrange parameters.Comment: 52 pages + 4 figures; accepted for publication in Physical Review
A many-body perturbation theory approach to the electron-phonon interaction with density-functional theory as a starting point
The electron-phonon interaction plays a crucial role in many fields of
physics and chemistry. Nevertheless, its actual calculation by means of modern
many-body perturbation theory is weakened by the use of model Hamiltonians that
are based on parameters difficult to extract from the experiments. Such
shortcoming can be bypassed by using density-functional theory to evaluate the
electron-phonon scattering amplitudes, phonon frequencies and electronic bare
energies. In this work, we discuss how a consistent many-body diagrammatic
expansion can be constructed on top of density-functional theory. In that
context, the role played by screening and self-consistency when all the
components of the electron-nucleus and nucleus-nucleus interactions are taken
into account is paramount. A way to avoid over-screening is notably presented.
Finally, we derive cancellations rules as well as internal consistency
constraints in order to draw a clear, sound and practical scheme to merge
many-body perturbation and density-functional theory.Comment: 25 pages, 13 figure
Ab initio Study of Luminescence in Ce-doped LuSiO: The Role of Oxygen Vacancies on Emission Color and Thermal Quenching Behavior
We study from first principles the luminescence of LuSiO:Ce
(LSO:Ce), a scintillator widely used in medical imaging applications, and
establish the crucial role of oxygen vacancies (V) in the generated
spectrum. The excitation energy, emission energy and Stokes shift of its
luminescent centers are simulated through a constrained density-functional
theory method coupled with a SCF analysis of total energies, and
compared with experimental spectra. We show that the high-energy emission band
comes from a single Ce-based luminescent center, while the large experimental
spread of the low-energy emission band originates from a whole set of different
Ce-V complexes together with the other Ce-based luminescent center.
Further, the luminescence thermal quenching behavior is analyzed. The
crossover mechanism is found to be very unlikely, with a large crossing energy
barrier (E) in the one-dimensional model. The alternative mechanism
usually considered, namely the electron auto-ionization, is also shown to be
unlikely. In this respect, we introduce a new methodology in which the
time-consuming accurate computation of the band gap for such models is
bypassed. We emphasize the usually overlooked role of the differing geometry
relaxation in the excited neutral electronic state Ce and in the
ionized electronic state Ce. The results indicate that such electron
auto-ionization cannot explain the thermal stability difference between the
high- and low-energy emission bands. Finally, a hole auto-ionization process is
proposed as a plausible alternative. With the already well-established excited
state characterization methodology, the approach to color center identification
and thermal quenching analysis proposed here can be applied to other
luminescent materials in the presence of intrinsic defects.Comment: 13 pages, 8 figures, accepted by Phys. Rev. Material
Convergence and pitfalls of density functional perturbation theory phonons calculations from a high-throughput perspective
The diffusion of large databases collecting different kind of material
properties from high-throughput density functional theory calculations has
opened new paths in the study of materials science thanks to data mining and
machine learning techniques. Phonon calculations have already been employed
successfully to predict materials properties and interpret experimental data,
e.g. phase stability, ferroelectricity and Raman spectra, so their availability
for a large set of materials will further increase the analytical and
predictive power at hand. Moving to a larger scale with density functional
perturbation calculations, however, requires the presence of a robust framework
to handle this challenging task. In light of this, we automatized the phonon
calculation and applied the result to the analysis of the convergence trends
for several materials. This allowed to identify and tackle some common problems
emerging in this kind of simulations and to lay out the basis to obtain
reliable phonon band structures from high-throughput calculations, as well as
optimizing the approach to standard phonon simulations
First-principles study of Ce doped lanthanum silicate nitride phosphors: Neutral excitation, Stokes shift, and luminescent center identification
We study from first principles two lanthanum silicate nitride compounds,
LaSiN and LaSiN, pristine as well as doped with
Ce ion, in view of explaining their different emission color, and
characterising the luminescent center. The electronic structures of the two
undoped hosts are similar, and do not give a hint to quantitatively describe
such difference. The neutral excitation of the Ce
ions is simulated through a constrained density-functional theory method
coupled with a SCF analysis of total energies, yielding absorption
energies. Afterwards, atomic positions in the excited state are relaxed,
yielding the emission energies and Stokes shifts. Based on these results, the
luminescent centers in LaSiN:Ce and LaSiN:Ce are
identified. The agreement with the experimental data for the computed
quantities is quite reasonable and explains the different color of the emitted
light. Also, the Stokes shifts are obtained within 20\% difference relative to
experimental data.Comment: 12 pages, 10 figure
First-principles Study of the Luminescence of Eu2+-doped Phosphors
The luminescence of fifteen representative Eu-doped phosphors used for
white-LED and scintillation applications is studied through a Constrained
Density Functional Theory. Transition energies and Stokes shift are deduced
from differences of total energies between the ground and excited states of the
systems, in the absorption and emission geometries. The general applicability
of such methodology is first assessed: for this representative set, the
calculated absolute error with respect to experiment on absorption and emission
energies is within 0.3 eV. This set of compounds covers a wide range of
transition energies that extents from 1.7 to 3.5 eV. The information gained
from the relaxed geometries and total energies is further used to evaluate the
thermal barrier for the crossover, the full width at half-maximum of
the emission spectrum and the temperature shift of the emission peak, using a
one-dimensional configuration-coordinate model. The former results indicate
that the crossover cannot be the dominant mechanism for the thermal
quenching behavior of Eu-doped phosphors and the latter results are
compared to available experimental data and yield a 30 mean absolute
relative error. Finally, a semi-empirical model used previously for
Ce-doped hosts is adapted to Eu-doped hosts and gives the
absorption and emission energies within 0.9 eV of experiment, underperforming
compared to the first-principles calculation.Comment: 17 pages, 13 figures, (Phys. Rev. B 2017 Accept
Ab Initio Approach to Second-order Resonant Raman Scattering Including Exciton-Phonon Interaction
Raman spectra obtained by the inelastic scattering of light by crystalline
solids contain contributions from first-order vibrational processes (e.g. the
emission or absorption of one phonon, a quantum of vibration) as well as
higher-order processes with at least two phonons being involved. At second
order, coupling with the entire phonon spectrum induces a response that may
strongly depend on the excitation energy, and reflects complex processes more
difficult to interpret. In particular, excitons (i.e. bound electron-hole
pairs) may enhance the absorption and emission of light, and couple strongly
with phonons in resonance conditions. We design and implement a
first-principles methodology to compute second-order Raman scattering,
incorporating dielectric responses and phonon eigenstates obtained from
density-functional theory and many-body theory. We demonstrate our approach for
the case of silicon, relating frequency-dependent relative Raman intensities,
that are in excellent agreement with experiment, to different vibrations and
regions of the Brillouin zone. We show that exciton-phonon coupling, computed
from first principles, indeed strongly affect the spectrum in resonance
conditions. The ability to analyze second-order Raman spectra thus provides
direct insight into this interaction.Comment: 10 pages, 8 figure
Assessment of First-Principles and Semiempirical Methodologies for Absorption and Emission Energies of Ce-Doped Luminescent Materials
In search of a reliable methodology for the prediction of light absorption
and emission of Ce-doped luminescent materials, 13 representative
materials are studied with first-principles and semiempirical approaches. In
the first-principles approach, that combines constrained density-functional
theory and SCF, the atomic positions are obtained for both ground and
excited states of the Ce ion. The structural information is fed into
Dorenbos' semiempirical model. Absorption and emission energies are calculated
with both methods and compared with experiment. The first-principles approach
matches experiment within 0.3 eV, with two exceptions at 0.5 eV. In contrast,
the semiempirical approach does not perform as well (usually more than 0.5 eV
error). The general applicability of the present first-principles scheme, with
an encouraging predictive power, opens a novel avenue for crystal site
engineering and high-throughput search for new phosphors and scintillators.Comment: 12 pages, 3 figure
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