435 research outputs found
Excitation energies from density functional perturbation theory
We consider two perturbative schemes to calculate excitation energies, each
employing the Kohn-Sham Hamiltonian as the unperturbed system. Using accurate
exchange-correlation potentials generated from essentially exact densities and
their exchange components determined by a recently proposed method, we evaluate
energy differences between the ground state and excited states in first-order
perturbation theory for the Helium, ionized Lithium and Beryllium atoms. It was
recently observed that the zeroth-order excitations energies, simply given by
the difference of the Kohn-Sham eigenvalues, almost always lie between the
singlet and triplet experimental excitations energies, corrected for
relativistic and finite nuclear mass effects. The first-order corrections
provide about a factor of two improvement in one of the perturbative schemes
but not in the other. The excitation energies within perturbation theory are
compared to the excitations obtained within SCF and time-dependent
density functional theory. We also calculate the excitation energies in
perturbation theory using approximate functionals such as the local density
approximation and the optimized effective potential method with and without the
Colle-Salvetti correlation contribution
Electron localization : band-by-band decomposition, and application to oxides
Using a plane wave pseudopotential approach to density functional theory we
investigate the electron localization length in various oxides. For this
purpose, we first set up a theory of the band-by-band decomposition of this
quantity, more complex than the decomposition of the spontaneous polarization
(a related concept), because of the interband coupling. We show its
interpretation in terms of Wannier functions and clarify the effect of the
pseudopotential approximation. We treat the case of different oxides: BaO,
-PbO, BaTiO and PbTiO. We also investigate the variation of the
localization tensor during the ferroelectric phase transitions of BaTiO as
well as its relationship with the Born effective charges
Non-linear optical susceptibilities, Raman efficiencies and electrooptic tensors from first-principles density functional perturbation theory
The non-linear response of infinite periodic solids to homogenous electric
fields and collective atomic displacements is discussed in the framework of
density functional perturbation theory. The approach is based on the 2n + 1
theorem applied to an electric-field-dependent energy functional. We report the
expressions for the calculation of the non-linear optical susceptibilities,
Raman scattering efficiencies and electrooptic coefficients. Different
formulations of third-order energy derivatives are examined and their
convergence with respect to the k-point sampling is discussed. We apply our
method to a few simple cases and compare our results to those obtained with
distinct techniques. Finally, we discuss the effect of a scissors correction on
the EO coefficients and non-linear optical susceptibilities
Specification of an extensible and portable file format for electronic structure and crystallographic data
In order to allow different software applications, in constant evolution, to
interact and exchange data, flexible file formats are needed. A file format
specification for different types of content has been elaborated to allow
communication of data for the software developed within the European Network of
Excellence "NANOQUANTA", focusing on first-principles calculations of materials
and nanosystems. It might be used by other software as well, and is described
here in detail. The format relies on the NetCDF binary input/output library,
already used in many different scientific communities, that provides
flexibility as well as portability accross languages and platforms. Thanks to
NetCDF, the content can be accessed by keywords, ensuring the file format is
extensible and backward compatible
Lattice Properties of PbX (X = S, Se, Te): Experimental Studies and ab initio Calculations Including Spin-Orbit Effects
During the past five years the low temperature heat capacity of simple
semiconductors and insulators has received renewed attention. Of particular
interest has been its dependence on isotopic masses and the effect of spin-
orbit coupling in ab initio calculations. Here we concentrate on the lead
chalcogenides PbS, PbSe and PbTe. These materials, with rock salt structure,
have different natural isotopes for both cations and anions, a fact that allows
a systematic experimental and theoretical study of isotopic effects e.g. on the
specific heat. Also, the large spin-orbit splitting of the 6p electrons of Pb
and the 5p of Te allows, using a computer code which includes spin-orbit
interaction, an investigation of the effect of this interaction on the phonon
dispersion relations and the temperature dependence of the specific heat and on
the lattice parameter. It is shown that agreement between measurements and
calculations significantly improves when spin-orbit interaction is included.Comment: 25 pages, 12 Figures, 1 table, submitted to PR
Ab initio studies of phonon softening and high pressure phase transitions of alpha-quartz SiO2
Density functional perturbation theory calculations of alpha-quartz using
extended norm conserving pseudopotentials have been used to study the elastic
properties and phonon dispersion relations along various high symmetry
directions as a function of bulk, uniaxial and non-hydrostatic pressure. The
computed equation of state, elastic constants and phonon frequencies are found
to be in good agreement with available experimental data. A zone boundary (1/3,
1/3, 0) K-point phonon mode becomes soft for pressures above P=32 GPa. Around
the same pressure, studies of the Born stability criteria reveal that the
structure is mechanically unstable. The phonon and elastic softening are
related to the high pressure phase transitions and amorphization of quartz and
these studies suggest that the mean transition pressure is lowered under
non-hydrostatic conditions. Application of uniaxial pressure, results in a
post-quartz crystalline monoclinic C2 structural transition in the vicinity of
the K-point instability. This structure, intermediate between quartz and
stishovite has two-thirds of the silicon atoms in octahedral coordination while
the remaining silicon atoms remain tetrahedrally coordinated. This novel
monoclinic C2 polymorph of silica, which is found to be metastable under
ambient conditions, is possibly one of the several competing dense forms of
silica containing octahedrally coordinated silicon. The possible role of high
pressure ferroelastic phases in causing pressure induced amorphization in
silica are discussed.Comment: 17 pages, 8 figs., 8 Table
Structural and dielectric properties of SrTiO from first principles
We have investigated the structural and dielectric properties of
SrTiO,the first member of the SrTiO
Ruddlesden-Popper series, within density functional theory. Motivated by recent
work in which thin films of SrTiO were grown by molecular beam
epitaxy (MBE) on SrTiO substrates, the in-plane lattice parameter was
fixed to the theoretically optimized lattice constant of cubic SrTiO
(n=), while the out-of-plane lattice parameter and the internal
structural parameters were relaxed. The fully relaxed structure was also
investigated. Density functional perturbation theory was used to calculate the
zone-center phonon frequencies, Born effective charges, and the electronic
dielectric permittivity tensor. A detailed study of the contribution of
individual infrared-active modes to the static dielectric permittivity tensor
was performed. The calculated Raman and infrared phonon frequencies were found
to be in agreement with experiment where available. Comparisons of the
calculated static dielectric permittivity with experiments on both ceramic
powders and epitaxial thin films are discussed.Comment: 11 pages, 1 figure, 8 tables, submitted to Phys. Rev.
An efficient k.p method for calculation of total energy and electronic density of states
An efficient method for calculating the electronic structure in large systems
with a fully converged BZ sampling is presented. The method is based on a
k.p-like approximation developed in the framework of the density functional
perturbation theory. The reliability and efficiency of the method are
demostrated in test calculations on Ar and Si supercells
Exciton-plasmon states in nanoscale materials: breakdown of the Tamm-Dancoff approximation
Within the Tamm-Dancoff approximation ab initio approaches describe excitons
as packets of electron-hole pairs propagating only forward in time. However, we
show that in nanoscale materials excitons and plasmons hybridize, creating
exciton--plasmon states where the electron-hole pairs oscillate back and forth
in time. Then, as exemplified by the trans-azobenzene molecule and carbon
nanotubes, the Tamm-Dancoff approximation yields errors as large as the
accuracy claimed in ab initio calculations. Instead, we propose a general and
efficient approach that avoids the Tamm--Dancoff approximation, and correctly
describes excitons, plasmons and exciton-plasmon states
- …