397 research outputs found
Managing the supercell approximation for charged defects in semiconductors: finite size scaling, charge correction factors, the bandgap problem and the ab initio dielectric constant
The errors arising in ab initio density functional theory studies of
semiconductor point defects using the supercell approximation are analyzed. It
is demonstrated that a) the leading finite size errors are inverse linear and
inverse cubic in the supercell size, and b) finite size scaling over a series
of supercells gives reliable isolated charged defect formation energies to
around +-0.05 eV. The scaled results are used to test three correction methods.
The Makov-Payne method is insufficient, but combined with the scaling
parameters yields an ab initio dielectric constant of 11.6+-4.1 for InP. Gamma
point corrections for defect level dispersion are completely incorrect, even
for shallow levels, but re-aligning the total potential in real-space between
defect and bulk cells actually corrects the electrostatic defect-defect
interaction errors as well. Isolated defect energies to +-0.1 eV are then
obtained using a 64 atom supercell, though this does not improve for larger
cells. Finally, finite size scaling of known dopant levels shows how to treat
the band gap problem: in less than about 200 atom supercells with no
corrections, continuing to consider levels into the theoretical conduction band
(extended gap) comes closest to experiment. However, for larger cells or when
supercell approximation errors are removed, a scissors scheme stretching the
theoretical band gap onto the experimental one is in fact correct.Comment: 11 pages, 3 figures (6 figure files). Accepted for Phys Rev
Structure and apparent topography of TiO2 (110) surfaces
We present self-consistent ab-initio total-energy and electronic-structure
calculations on stoichiometric and non-stoichiometric TiO2 (110) surfaces.
Scanning tunneling microscopy (STM) topographs are simulated by calculating the
local electronic density of states over an energy window appropriate for the
experimental positive-bias conditions. We find that under these conditions the
STM tends to image the undercoordinated Ti atoms, in spite of the physical
protrusion of the O atoms, giving an apparent reversal of topographic contrast
on the stoichiometric 1x1 or missing-row 2x1 surface. We also show that both
the interpretation of STM images and the direct comparison of surface energies
favor an added-row structure over the missing-row structure for the
oxygen-deficient 2x1 surface.Comment: 6 pages, two-column style with 5 postscript figures embedded. Uses
REVTEX and epsf macros. Also available at
http://www.physics.rutgers.edu/~dhv/preprints/index.html#ng_tio
Variational finite-difference representation of the kinetic energy operator
A potential disadvantage of real-space-grid electronic structure methods is
the lack of a variational principle and the concomitant increase of total
energy with grid refinement. We show that the origin of this feature is the
systematic underestimation of the kinetic energy by the finite difference
representation of the Laplacian operator. We present an alternative
representation that provides a rigorous upper bound estimate of the true
kinetic energy and we illustrate its properties with a harmonic oscillator
potential. For a more realistic application, we study the convergence of the
total energy of bulk silicon using a real-space-grid density-functional code
and employing both the conventional and the alternative representations of the
kinetic energy operator.Comment: 3 pages, 3 figures, 1 table. To appear in Phys. Rev. B. Contribution
for the 10th anniversary of the eprint serve
First-principles study of spontaneous polarization in multiferroic BiFeO
The ground-state structural and electronic properties of ferroelectric
BiFeO are calculated using density functional theory within the local
spin-density approximation and the LSDA+U method. The crystal structure is
computed to be rhombohedral with space group , and the electronic
structure is found to be insulating and antiferromagnetic, both in excellent
agreement with available experiments. A large ferroelectric polarization of
90-100 C/cm is predicted, consistent with the large atomic
displacements in the ferroelectric phase and with recent experimental reports,
but differing by an order of magnitude from early experiments. One possible
explanation is that the latter may have suffered from large leakage currents.
However both past and contemporary measurements are shown to be consistent with
the modern theory of polarization, suggesting that the range of reported
polarizations may instead correspond to distinct switching paths in structural
space. Modern measurements on well-characterized bulk samples are required to
confirm this interpretation.Comment: (9 pages, 5 figures, 5 tables
Heterovalent and A-atom effects in A(B'B'')O3 perovskite alloys
Using first-principles supercell calculations, we have investigated
energetic, structural and dielectric properties of three different A(B'B'')O_3
perovskite alloys: Ba(Zn_{1/3}Nb_{2/3})O_3 (BZN), Pb(Zn_{1/3}Nb_{2/3})O_3
(PZN), and Pb(Zr_{1/3}Ti_{2/3})O_3 (PZT). In the homovalent alloy PZT, the
energetics are found to be mainly driven by atomic relaxations. In the
heterovalent alloys BZN and PZN, however, electrostatic interactions among B'
and B'' atoms are found to be very important. These electrostatic interactions
are responsible for the stabilization of the observed compositional long-range
order in BZN. On the other hand, cell relaxations and the formation of short
Pb--O bonds could lead to a destabilization of the same ordered structure in
PZN. Finally, comparing the dielectric properties of homovalent and
heterovalent alloys, the most dramatic difference arises in connection with the
effective charges of the B' atom. We find that the effective charge of Zr in
PZT is anomalous, while in BZN and PZN the effective charge of Zn is close to
its nominal ionic value.Comment: 7 pages, two-column style with 2 postscript figures embedded. Uses
REVTEX and epsf macros. Also available at
http://www.physics.rutgers.edu/~dhv/preprints/index.html#lb_he
Energetics of hydrogen impurities in aluminum and their effect on mechanical properties
The effects of hydrogen impurities in the bulk and on the surface of aluminum
are theoretically investigated. Within the framework of density functional
theory, we have obtained the dependence on H concentration of the stacking
fault energy, the cleavage energy, the Al/H surface energy and the Al/H/Al
interface formation energy. The results indicate a strong dependence of the
slip energy barrier in the direction the cleavage energy in the
[111] direction and the Al/H/Al interface formation energy, on H concentration
and on tension. The dependence of the Al/H surface energy on H coverage is less
pronounced, while the optimal H coverage is monolayer. The
calculated activation energy for diffusion between high symmetry sites in the
bulk and on the surface is practically the same, 0.167 eV. From these results,
we draw conclusions about the possible effect of H impurities on mechanical
properties, and in particular on their role in embrittlement of Al.Comment: 9 pages, 5 figure
Relative concentration and structure of native defects in GaP
The native defects in the compound semiconductor GaP have been studied using a pseudopotential density functional theory method in order to determine their relative concentrations and the most stable charge states. The electronic and atomic structures are presented and the defect concentrations are estimated using calculated formation energies. Relaxation effects are taken into account fully and produce negative-U charge transfer levels for VP and PGa. The concentration of VGa is in good agreement with the results of positron annihilation experiments. The charge transfer levels presented compare qualitatively well with experiments where available. The effect of stoichiometry on the defect concentrations is also described and is shown to be considerable. The lowest formation energies are found for PGa +2 in p-type and VGa −3 in n-type GaP under P-rich conditions, and for GaP −2 in n-type GaP under Ga-rich conditions. Finally, the finite size errors arising from the use of supercells with periodic boundary conditions are examined
First-principles study of the structural energetics of PdTi and PtTi
The structural energetics of PdTi and PtTi have been studied using
first-principles density-functional theory with pseudopotentials and a
plane-wave basis. We predict that in both materials, the experimentally
reported orthorhombic phase will undergo a low-temperature phase
transition to a monoclinic ground state. Within a soft-mode framework,
we relate the structure to the cubic structure, observed at high
temperature, and the structure to via phonon modes strongly
coupled to strain. In contrast to NiTi, the structure is extremely close
to hcp. We draw on the analogy to the bcc-hcp transition to suggest likely
transition mechanisms in the present case.Comment: 8 pages 5 figure
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