48 research outputs found
Symmetry of the Atomic Electron Density in Hartree, Hartree-Fock, and Density Functional Theory
The density of an atom in a state of well-defined angular momentum has a
specific finite spherical harmonic content, without and with interactions.
Approximate single-particle schemes, such as the Hartree, Hartree-Fock, and
Local Density Approximations, generally violate this feature. We analyze, by
means of perturbation theory, the degree of this violation and show that it is
small. The correct symmetry of the density can be assured by a
constrained-search formulation without significantly altering the calculated
energies. We compare our procedure to the (different) common practice of
spherically averaging the self-consistent potential. Kohn-Sham density
functional theory with the exact exchange-correlation potential has the correct
finite spherical harmonic content in its density; but the corresponding exact
single particle potential and wavefunctions contain an infinite number of
spherical harmonics.Comment: 11 pages, 6 figures. Expanded discussion of spherical harmonic
expansion of Hartree density. Some typos corrected, references adde
RPA vs. exact shell-model correlation energies
The random phase approximation (RPA) builds in correlations left out by
mean-field theory. In full 0-hbar-omega shell-model spaces we calculate the
Hartree-Fock + RPA binding energy, and compare it to exact diagonalization. We
find that in general HF+RPA gives a very good approximation to the ``exact''
ground state energy. In those cases where RPA is less satisfactory, however,
there is no obvious correlation with properties of the HF state, such as
deformation or overlap with the exact ground state wavefunction.Comment: 6 pages, 7 figures, submitted to Phys Rev
Density-functional theory of quantum wires and dots in a strong magnetic field
We study the competition between the exchange and the direct Coulomb
interaction near the edge of a two-dimensional electron gas in a strong
magnetic field using density-functional theory in a local approximation for the
exchange-energy functional. Exchange is shown to play a significant role in
reducing the spatial extent of the compressible edge channel regions obtained
from an electrostatic description. The transition from the incompressible edge
channels of the Hartree-Fock picture to the broad, compressible strips
predicted by electrostatics occurs within a narrow and experimentally
accessible range of confinement strengths.Comment: 24 pages latex and 10 postscript figures in self extracting fil
Quasi-Local Density Functional Theory and its Application within Extended Thomas-Fermi Approximation
A generalization of the Density Functional Theory is proposed. The theory
developed leads to single-particle equations of motion with a quasi-local
mean-field operator, which contains a quasi-particle position-dependent
effective mass and a spin-orbit potential. The energy density functional is
constructed using the Extended Thomas-Fermi approximation. Within the framework
of this approach the ground-state properties of the doubly magic nuclei are
considered. The calculations have been performed using the finite-range Gogny
D1S force. The results are compared with the exact Hartree-Fock calculations
Relativistic corrections in magnetic systems
We present a weak-relativistic limit comparison between the Kohn-Sham-Dirac
equation and its approximate form containing the exchange coupling, which is
used in almost all relativistic codes of density-functional theory. For these
two descriptions, an exact expression of the Dirac Green's function in terms of
the non-relativistic Green's function is first derived and then used to
calculate the effective Hamiltonian, i.e., Pauli Hamiltonian, and effective
velocity operator in the weak-relativistic limit. We point out that, besides
neglecting orbital magnetism effects, the approximate Kohn-Sham-Dirac equation
also gives relativistic corrections which differ from those of the exact
Kohn-Sham-Dirac equation. These differences have quite serious consequences: in
particular, the magnetocrystalline anisotropy of an uniaxial ferromagnet and
the anisotropic magnetoresistance of a cubic ferromagnet are found from the
approximate Kohn-Sham-Dirac equation to be of order , whereas the
correct results obtained from the exact Kohn-Sham-Dirac equation are of order
. We give a qualitative estimate of the order of magnitude of these
spurious terms
Occupation numbers in density-functional calculations
It is the intention of this paper to rigorously clarify the role of the
occupation numbers in the current practical applications of the density
functional formalism. In these calculations one has to decide how to distribute
a given, fixed number of electrons over a set of single-particle orbitals. The
conventional choice is to have orbitals below the Fermi level completely
occupied and the orbitals above the Fermi level empty. Although there is a
certain confusion in literature why this choice is superior to any others, the
general belief is that it can justified by treating the occupation numbers as
variational parameters and then applying Janak's theorem or similar reasoning.
We demonstrate that there is a serious flaw in those arguments,mainly the
kinetic energy and therefore the exchange-correlation potential are not
differentiable with respect to density for arbitrary occupation numbers. It is
rigorously shown that in the present context of the density functional
calculations there is no freedom to vary the occupation numbers. The occupation
numbers cannot be considered as variational parameters.Comment: 10 pages, Revtex, accepted for publication by Phys.Rev.
Scaling analysis of electron transport through metal-semiconducting carbon nanotube interfaces: Evolution from the molecular limit to the bulk limit
We present a scaling analysis of electronic and transport properties of
metal-semiconducting carbon nanotube interfaces as a function of the nanotube
length within the coherent transport regime, which takes fully into account
atomic-scale electronic structure and three-dimensional electrostatics of the
metal-nanotube interface using a real-space Green's function based
self-consistent tight-binding theory. As the first example, we examine devices
formed by attaching finite-size single-wall carbon nanotubes (SWNT) to both
high- and low- work function metallic electrodes through the dangling bonds at
the end. We analyze the nature of Schottky barrier formation at the
metal-nanotube interface by examining the electrostatics, the band lineup and
the conductance of the metal-SWNT molecule-metal junction as a function of the
SWNT molecule length and metal-SWNT coupling strength. We show that the
confined cylindrical geometry and the atomistic nature of electronic processes
across the metal-SWNT interface leads to a different physical picture of band
alignment from that of the planar metal-semiconductor interface. We analyze the
temperature and length dependence of the conductance of the SWNT junctions,
which shows a transition from tunneling- to thermal activation-dominated
transport with increasing nanotube length. The temperature dependence of the
conductance is much weaker than that of the planar metal-semiconductor
interface due to the finite number of conduction channels within the SWNT
junctions. We find that the current-voltage characteristics of the metal-SWNT
molecule-metal junctions are sensitive to models of the potential response to
the applied source/drain bias voltages.Comment: Minor revision to appear in Phys. Rev. B. Color figures available in
the online PRB version or upon request to: [email protected]
Systematics of collective correlation energies from self-consistent mean-field calculations
The collective ground-state correlations stemming from low-lying quadrupole
excitations are computed microscopically. To that end, the self-consistent
mean-field model is employed on the basis of the Skyrme-Hartre-Fock (SHF)
functional augmented by BCS pairing. The microscopic-macroscopic mapping is
achieved by quadrupole-constrained mean-field calculations which are processed
further in the generator-coordinate method (GCM) at the level of the Gaussian
overlap approximation (GOA).
We study the correlation effects on energy, charge radii, and surface
thickness for a great variety of semi-magic nuclei. A key issue is to work out
the influence of variations of the SHF functional. We find that collective
ground-state correlations (GSC) are robust under change of nuclear bulk
properties (e.g., effective mass, symmetry energy) or of spin-orbit coupling.
Some dependence on the pairing strength is observed. This, however, does not
change the general conclusion that collective GSC obey a general pattern and
that their magnitudes are rather independent of the actual SHF parameters.Comment: 13 pages, 13 figure
Thermal Density Functional Theory in Context
This chapter introduces thermal density functional theory, starting from the
ground-state theory and assuming a background in quantum mechanics and
statistical mechanics. We review the foundations of density functional theory
(DFT) by illustrating some of its key reformulations. The basics of DFT for
thermal ensembles are explained in this context, as are tools useful for
analysis and development of approximations. We close by discussing some key
ideas relating thermal DFT and the ground state. This review emphasizes thermal
DFT's strengths as a consistent and general framework.Comment: Submitted to Spring Verlag as chapter in "Computational Challenges in
Warm Dense Matter", F. Graziani et al. ed
Ab initio atomistic thermodynamics and statistical mechanics of surface properties and functions
Previous and present "academic" research aiming at atomic scale understanding
is mainly concerned with the study of individual molecular processes possibly
underlying materials science applications. Appealing properties of an
individual process are then frequently discussed in terms of their direct
importance for the envisioned material function, or reciprocally, the function
of materials is somehow believed to be understandable by essentially one
prominent elementary process only. What is often overlooked in this approach is
that in macroscopic systems of technological relevance typically a large number
of distinct atomic scale processes take place. Which of them are decisive for
observable system properties and functions is then not only determined by the
detailed individual properties of each process alone, but in many, if not most
cases also the interplay of all processes, i.e. how they act together, plays a
crucial role. For a "predictive materials science modeling with microscopic
understanding", a description that treats the statistical interplay of a large
number of microscopically well-described elementary processes must therefore be
applied. Modern electronic structure theory methods such as DFT have become a
standard tool for the accurate description of individual molecular processes.
Here, we discuss the present status of emerging methodologies which attempt to
achieve a (hopefully seamless) match of DFT with concepts from statistical
mechanics or thermodynamics, in order to also address the interplay of the
various molecular processes. The new quality of, and the novel insights that
can be gained by, such techniques is illustrated by how they allow the
description of crystal surfaces in contact with realistic gas-phase
environments.Comment: 24 pages including 17 figures, related publications can be found at
http://www.fhi-berlin.mpg.de/th/paper.htm