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 $1/c^2$, whereas the correct results obtained from the exact Kohn-Sham-Dirac equation are of order $1/c^4$ . 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