161 research outputs found
Benchmarking GW against exact diagonalization for semi-empirical models
We calculate groundstate total energies and single-particle excitation
energies of seven pi conjugated molecules described with the semi-empirical
Pariser-Parr-Pople (PPP) model using self-consistent many-body perturbation
theory at the GW level and exact diagonalization. For the total energies GW
captures around 65% of the groundstate correlation energy. The lowest lying
excitations are overscreened by GW leading to an underestimation of electron
affinities and ionization potentials by approximately 0.15 eV corresponding to
2.5%. One-shot G_0W_0 calculations starting from Hartree-Fock reduce the
screening and improve the low-lying excitation energies. The effect of the GW
self-energy on the molecular excitation energies is shown to be similar to the
inclusion of final state relaxations in Hartree-Fock theory. We discuss the
break down of the GW approximation in systems with short range interactions
(Hubbard models) where correlation effects dominate over screening/relaxation
effects. Finally we illustrate the important role of the derivative
discontinuity of the true exchange-correlation functional by computing the
exact Kohn-Sham levels of benzene.Comment: 9 pages, 5 figures, accepted for publication in Phys. Rev.
Quasiparticle band structure based on a generalized Kohn-Sham scheme
We present a comparative full-potential study of generalized Kohn-Sham
schemes (gKS) with explicit focus on their suitability as starting point for
the solution of the quasiparticle equation. We compare quasiparticle
band structures calculated upon LDA, sX, HSE03, PBE0, and HF functionals for
exchange and correlation (XC) for Si, InN and ZnO. Furthermore, the HSE03
functional is studied and compared to the GGA for 15 non-metallic materials for
its use as a starting point in the calculation of quasiparticle excitation
energies. For this case, also the effects of selfconsistency in the
self-energy are analysed. It is shown that the use of a gKS scheme as a
starting point for a perturbative QP correction can improve upon the
deficiencies found for LDA or GGA staring points for compounds with shallow
bands. For these solids, the order of the valence and conduction bands is often
inverted using local or semi-local approximations for XC, which makes
perturbative calculations unreliable. The use of a gKS starting point
allows for the calculation of fairly accurate band gaps even in these difficult
cases, and generally single-shot calculations following calculations
using the HSE03 functional are very close to experiment
Quasiparticle Self-Consistent GW Theory
In past decades the scientific community has been looking for a reliable
first-principles method to predict the electronic structure of solids with high
accuracy. Here we present an approach which we call the quasiparticle
self-consistent GW approximation (QpscGW). It is based on a kind of
self-consistent perturbation theory, where the self-consistency is constructed
to minimize the perturbation. We apply it to selections from different classes
of materials, including alkali metals, semiconductors, wide band gap
insulators, transition metals, transition metal oxides, magnetic insulators,
and rare earth compounds. Apart some mild exceptions, the properties are very
well described, particularly in weakly correlated cases. Self-consistency
dramatically improves agreement with experiment, and is sometimes essential.
Discrepancies with experiment are systematic, and can be explained in terms of
approximations made.Comment: 12 pages, 3 figure
Ultrathin oxides: bulk-oxide-like model surfaces or unique films?
To better understand the electronic and chemical properties of wide-gap oxide
surfaces at the atomic scale, experimental work has focused on epitaxial films
on metal substrates. Recent findings show that these films are considerably
thinner than previously thought. This raises doubts about the transferability
of the results to surface properties of thicker films and bulk crystals. By
means of density-functional theory and approximate GW corrections for the
electronic spectra we demonstrate for three characteristic wide-gap oxides
(silica, alumina, and hafnia) the influence of the substrate and highlight
critical differences between the ultrathin films and surfaces of bulk
materials. Our results imply that monolayer-thin oxide films have rather unique
properties.Comment: 5 pages, 3 figures, accepted by PR
Electron-phonon coupling in the C60 fullerene within the many-body GW approach
We study the electron-phonon coupling in the C60 fullerene within the
first-principles GW approach, focusing on the lowest unoccupied t1u three-fold
electronic state which is relevant for the superconducting transition in
electron doped fullerides. It is shown that the strength of the coupling is
significantly enhanced as compared to standard density functional theory
calculations with (semi)local functionals, with a 48% increase of the
electron-phonon potential Vep. The calculated GW value for the contribution
from the Hg modes of 93 meV comes within 4% of the most recent experimental
values. The present results call for a reinvestigation of previous density
functional based calculations of electron-phonon coupling in covalent systems
in general.Comment: 4 pages, 0 figur
GW approximation with self-screening correction
The \emph{GW} approximation takes into account electrostatic self-interaction
contained in the Hartree potential through the exchange potential. However, it
has been known for a long time that the approximation contains self-screening
error as evident in the case of the hydrogen atom. When applied to the hydrogen
atom, the \emph{GW} approximation does not yield the exact result for the
electron removal spectra because of the presence of self-screening: the hole
left behind is erroneously screened by the only electron in the system which is
no longer present. We present a scheme to take into account self-screening and
show that the removal of self-screening is equivalent to including exchange
diagrams, as far as self-screening is concerned. The scheme is tested on a
model hydrogen dimer and it is shown that the scheme yields the exact result to
second order in where and are respectively
the onsite and offsite Hubbard interaction parameters and the hopping
parameter.Comment: 9 pages, 2 figures; Submitted to Phys. Rev.
Density-density functionals and effective potentials in many-body electronic structure calculations
We demonstrate the existence of different density-density functionals
designed to retain selected properties of the many-body ground state in a
non-interacting solution starting from the standard density functional theory
ground state. We focus on diffusion quantum Monte Carlo applications that
require trial wave functions with optimal Fermion nodes. The theory is
extensible and can be used to understand current practices in several
electronic structure methods within a generalized density functional framework.
The theory justifies and stimulates the search of optimal empirical density
functionals and effective potentials for accurate calculations of the
properties of real materials, but also cautions on the limits of their
applicability. The concepts are tested and validated with a near-analytic
model.Comment: five figure
Quasiparticle Electronic structure of Copper in the GW approximation
We show that the results of photoemission and inverse photoemission
experiments on bulk copper can be quantitatively described within
band-structure theory, with no evidence of effects beyond the
single-quasiparticle approximation. The well known discrepancies between the
experimental bandstructure and the Kohn-Sham eigenvalues of Density Functional
Theory are almost completely corrected by self-energy effects.
Exchange-correlation contributions to the self-energy arising from 3s and 3p
core levels are shown to be crucial.Comment: 4 pages, 2 figures embedded in the text. 3 footnotes modified and 1
reference added. Small modifications also in the text. Accepted for
publication in PR
Interaction-Enhanced Coherence Between Two-Dimensional Dirac Layers
We estimate the strength of interaction-enhanced coherence between two
graphene or topological insulator surface-state layers by solving
imaginary-axis gap equations in the random phase approximation. Using a
self-consistent treatment of dynamic screening of Coulomb interactions in the
gapped phase, we show that the excitonic gap can reach values on the order of
the Fermi energy at strong interactions. The gap is discontinuous as a function
of interlayer separation and effective fine structure constant, revealing a
first order phase transition between effectively incoherent and interlayer
coherent phases. To achieve the regime of strong coherence the interlayer
separation must be smaller than the Fermi wavelength, and the extrinsic
screening of the medium embedding the Dirac layers must be negligible. In the
case of a graphene double-layer we comment on the supportive role of the remote
-bands neglected in the two-band Dirac model.Comment: 14 pages, 9 figure
The Band-Gap Problem in Semiconductors Revisited: Effects of Core States and Many-Body Self-Consistency
A novel picture of the quasiparticle (QP) gap in prototype semiconductors Si
and Ge emerges from an analysis based on all-electron, self-consistent, GW
calculations. The deep-core electrons are shown to play a key role via the
exchange diagram --if this effect is neglected, Si becomes a semimetal.
Contrary to current lore, the Ge 3d semicore states (e.g., their polarization)
have no impact on the GW gap. Self-consistency improves the calculated gaps --a
first clear-cut success story for the Baym-Kadanoff method in the study of
real-materials spectroscopy; it also has a significant impact on the QP
lifetimes. Our results embody a new paradigm for ab initio QP theory
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