10,732 research outputs found
Properties of short-range and long-range correlation energy density functionals from electron-electron coalescence
The combination of density functional theory with other approaches to the
many-electron problem through the separation of the electron-electron
interaction into a short-range and a long-range contribution is a promising
method, which is raising more and more interest in recent years. In this work
some properties of the corresponding correlation energy functionals are derived
by studying the electron-electron coalescence condition for a modified
(long-range-only) interaction. A general relation for the on-top (zero
electron-electron distance) pair density is derived, and its usefulness is
discussed with some examples. For the special case of the uniform electron gas,
a simple parameterization of the on-top pair density for a long-range only
interaction is presented and supported by calculations within the ``extended
Overhauser model''. The results of this work can be used to build
self-interaction corrected short-range correlation energy functionals.Comment: revised version, to appear in Phys. Rev.
Exchange energy in the local Airy gas approximation
The Airy gas model of the edge electron gas is used to construct an exchange-energy functional which is an alternative to those obtained in the local density and generalized gradient approximations. Test calculations for rare gas atoms, molecules, solids and surfaces show that the Airy gas functional performs better than the local density approximation in all cases and better than the generalized gradient approximation for solids and surfaces. Typeset using REVTEX 1 Since the pioneering papers on density functional theory (DFT) [1,2] there has been a constant search for exchange-correlation functionals of chemical accuracy. This includes the works on the generalized gradient approximation (GGA) [3–7] which are dedicated efforts to construct local functionals for inhomogeneous systems ranging from atoms to solids based on the uniform electron gas, i.e., the local density approximation (LDA), and density gradient corrections, as well as the development of a number gradien
Timesaving Double-Grid Method for Real-Space Electronic-Structure Calculations
We present a simple and efficient technique in ab initio electronic-structure
calculation utilizing real-space double-grid with a high density of grid points
in the vicinity of nuclei. This technique promises to greatly reduce the
overhead for performing the integrals that involves non-local parts of
pseudopotentials, with keeping a high degree of accuracy. Our procedure gives
rise to no Pulay forces, unlike other real-space methods using adaptive
coordinates. Moreover, we demonstrate the potential power of the method by
calculating several properties of atoms and molecules.Comment: 4 pages, 5 figure
Rearrangement of cluster structure during fission processes
Results of molecular dynamics simulations of fission reactions and are presented. Dependence
of the fission barriers on isomer structure of the parent cluster is analyzed.
It is demonstrated that the energy necessary for removing homothetic groups of
atoms from the parent cluster is largely independent of the isomer form of the
parent cluster. Importance of rearrangement of the cluster structure during the
fission process is elucidated. This rearrangement may include transition to
another isomer state of the parent cluster before actual separation of the
daughter fragments begins and/or forming a "neck" between the separating
fragments
Performance of ab initio and density functional methods for conformational equilibria of CnH2n+2 alkane isomers (n=2-8)
Conformational energies of n-butane, n-pentane, and n-hexane have been
calculated at the CCSD(T) level and at or near the basis set limit.
Post-CCSD(T) contribution were considered and found to be unimportant. The data
thus obtained were used to assess the performance of a variety of density
functional methods. Double-hybrid functionals like B2GP-PLYP and B2K-PLYP,
especially with a small Grimme-type empirical dispersion correction, are
capable of rendering conformational energies of CCSD(T) quality. These were
then used as a `secondary standard' for a larger sample of alkanes, including
isopentane and the branched hexanes as well as key isomers of heptane and
octane. Popular DFT functionals like B3LYP, B3PW91, BLYP, PBE, and PBE0 tend to
overestimate conformer energies without dispersion correction, while the M06
family severely underestimates GG interaction energies. Grimme-type dispersion
corrections for these overcorrect and lead to qualitatively wrong conformer
orderings. All of these functionals also exhibit deficiencies in the conformer
geometries, particularly the backbone torsion angles. The PW6B95 and, to a
lesser extent, BMK functionals are relatively free of these deficiencies.
Performance of these methods is further investigated to derive conformer
ensemble corrections to the enthalpy function, , and the Gibbs
energy function, , of these alkanes. While
is only moderately sensitive to the level of theory, exhibits more pronounced sensitivity. Once again, double hybrids
acquit themselves very well.Comment: J. Phys. Chem. A, revised [Walter Thiel festschrift
Performance of the modified Becke-Johnson potential
Very recently, in the 2011 version of the Wien2K code, the long standing
shortcome of the codes based on Density Functional Theory, namely, its
impossibility to account for the experimental band gap value of semiconductors,
was overcome. The novelty is the introduction of a new exchange and correlation
potential, the modified Becke-Johnson potential (mBJLDA). In this paper, we
report our detailed analysis of this recent work. We calculated using this
code, the band structure of forty one semiconductors and found an important
improvement in the overall agreement with experiment as Tran and Blaha [{\em
Phys. Rev. Lett.} 102, 226401 (2009)] did before for a more reduced set of
semiconductors. We find, nevertheless, within this enhanced set, that the
deviation from the experimental gap value can reach even much more than 20%, in
some cases. Furthermore, since there is no exchange and correlation energy term
from which the mBJLDA potential can be deduced, a direct optimization procedure
to get the lattice parameter in a consistent way is not possible as in the
usual theory. These authors suggest that a LDA or a GGA optimization procedure
is used previous to a band structure calculation and the resulting lattice
parameter introduced into the 2011 code. This choice is important since small
percentage differences in the lattice parameter can give rise to quite higher
percentage deviations from experiment in the predicted band gap value.Comment: 10 pages, 2 figures, 5 Table
Density functional electronic spectrum of the cluster and possible local Jahn-Teller distorsions in the La-Ba-Cu-O superconductor
We present a density functional theory (DFT) calculation in the generalized
gradient approximation to study the possibility for the existence of
Jahn-Teller (JT) or pseudo Jahn-Teller (PJT) type local distortions in the
La-Ba-Cu-O superconducting system. We performed the calculation and
correspondingly group theory classification of the electronic ground state of
the CuO elongated octahedra cluster, immersed in a background
simulating the superconductor. Part of the motivation to do this study is that
the origin of the apical deformation of the CuO cluster is not
due to a pure JT effect, having therefore a non {\it a priori} condition to
remove the degeneracy of the electronic ground state of the parent regular
octahedron. We present a comparative analysis of the symmetry classified
electron spectrum with previously reported results using unrestricted
Hartree-Fock calculations (UHF). Both the DFT and UHF calculations produced a
non degenerate electronic ground state, not having therefore the necessary
condition for a pure JT effect. However, the appearance of a degenerate E
state near to the highest occupied molecular orbital in the DFT calculation,
suggests the possibility for a PJT effect responsible for a local distortion of
the oxidized CuO cluster.Comment: 12 pages, 3 figures, submitted to International Journal of Modern
Physics B (IJMPB
Analysis of OPM potentials for multiplet states of 3d transition metal atoms
We apply the optimized effective potential method (OPM) to the multiplet
energies of the 3d transition metal atoms, where the orbital dependence of
the energy functional with respect to orbital wave function is the
single-configuration HF form. We find that the calculated OPM exchange
potential can be represented by the following two forms. Firstly, the
difference between OPM exchange potentials of the multiplet states can be
approximated by the linear combination of the potentials derived from the
Slater integrals and for the average
energy of the configuration. Secondly, the OPM exchange potential can be
expressed as the linear combination of the OPM exchange potentials of the
single determinants.Comment: 15 pages, 6 figures, to be published in J. Phys.
A Multiscale Approach to Determination of Thermal Properties and Changes in Free Energy: Application to Reconstruction of Dislocations in Silicon
We introduce an approach to exploit the existence of multiple levels of
description of a physical system to radically accelerate the determination of
thermodynamic quantities. We first give a proof of principle of the method
using two empirical interatomic potential functions. We then apply the
technique to feed information from an interatomic potential into otherwise
inaccessible quantum mechanical tight-binding calculations of the
reconstruction of partial dislocations in silicon at finite temperature. With
this approach, comprehensive ab initio studies at finite temperature will now
be possible.Comment: 5 pages, 3 figure
Pseudopotential study of binding properties of solids within generalized gradient approximations: The role of core-valence exchange-correlation
In ab initio pseudopotential calculations within density-functional theory
the nonlinear exchange-correlation interaction between valence and core
electrons is often treated linearly through the pseudopotential. We discuss the
accuracy and limitations of this approximation regarding a comparison of the
local density approximation (LDA) and generalized gradient approximations
(GGA), which we find to describe core-valence exchange-correlation markedly
different. (1) Evaluating the binding properties of a number of typical solids
we demonstrate that the pseudopotential approach and namely the linearization
of core-valence exchange-correlation are both accurate and limited in the same
way in GGA as in LDA. (2) Examining the practice to carry out GGA calculations
using pseudopotentials derived within LDA we show that the ensuing results
differ significantly from those obtained using pseudopotentials derived within
GGA. As principal source of these differences we identify the distinct behavior
of core-valence exchange-correlation in LDA and GGA which, accordingly,
contributes substantially to the GGA induced changes of calculated binding
properties.Comment: 13 pages, 6 figures, submitted to Phys. Rev. B, other related
publications can be found at http://www.rz-berlin.mpg.de/th/paper.htm
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