Potential functionals: dual to density functionals and solution to the v-representability problem

A functional of external potentials and its variational principle for the ground-state energy is constructed. This potential functional formulation is dual to the density functional approach and provides a solution to the v-representability problem in the original Hohenberg-Kohn theory. A second potential functional for Kohn-Sham noninteracting systems establishes the foundation for the optimized effective potential approach and results in efficient approaches for ensemble Kohn-Sham calculations.     

To the Theory of Inhomogeneous Electron Gas

Nonrigorous character of the density-functional theory for inhomogeneous electron gas based on the hypothesis assuming the existence of a universal density functional is demonstrated. A single-particle density matrix must be determined to calculate the ground-state energy of a finite system with a finite number of electrons. A single-particle Green function can be used to unambiguously determine the ground-state energy of an inhomogeneous electron system that satisfies the thermodynamic limit.     

On the semiconductor energy gap in density functional theory

The non-existence of the functional derivative of the Hohenberg-Kohn functional at the ground-state density of a semiconductor earlier discussed in the literature^2,3 is analyzed. Arguments are given that this non-existence is not connected with the discontinuity of the (ordinary) derivative of the functional with respect to the particle number N as discussed by Perdew and Levy².     

Remarks on the density functional approach to the inhomogeneous electron gas

The density functional approach is reformulated by using the most general form of the Hohenberg-Kohn theorem based on p-particle densities. Comparison with the reduced density matrix theory is made, exhibiting fully the p-particle hierarchy of both theories. Some advantages and drawbacks of the generalized density functional approach are discussed. The 1-particle spin-polarized case is presented to indicate the place of the usual DFA within the framework of the generalized theory.     

Density functional resonance theory of unbound electronic systems

Density functional resonance theory (DFRT) is a complex-scaled version of ground-state density functional theory (DFT) that allows one to calculate the in-principle exact resonance energies and lifetimes of metastable anions. In this formalism, the energy and lifetime of the lowest-energy resonance of unbound systems is encoded into a complex "density" that can be obtained via complex-coordinate scaling. This complex density is used as the primary variable in a DFRT calculation, just as the ground-state density would be used as the primary variable in DFT. As in DFT, there exists a mapping of the N-electron interacting system to a Kohn-Sham system of N noninteracting particles. This mapping facilitates self-consistent calculations with an initial guess for the complex density, as illustrated with an exactly solvable model system.     

Aluminum Hugoniot from model calculations including semicore electrons based on density functional theory

We present a method to obtain Hugoniot from model calculations based on density functional theory, and apply the method to aluminum Hugoniot. Technological advances have extended the experimental research of high energy density physics, and call for quantitative theoretical analysis. However, direct computation of Hugoniot from density functional theory is very difficult. We propose two step calculations of Hugoniot from density functional theory. The first step is molecular dynamics simulations with an ambient temperature for electrons. The second step is total energy calculations of a crystal with desired high temperatures for electrons and with the ambient temperature for electrons. We treated the semicore 2s and 2p electrons of aluminum as valence electrons only for the total energy calculations of the aluminum crystal. The aluminum Hugoniot from our model calculations is in excellent agreement with available experimental data and the previous density functional theory calculations in the literature.     

Application of density-functional perturbation theory to calculate nonlinear polarizabilities of helium-like systems

Density-based perturbation theory within the Hohenberg-Kohn (HK) formalism of density functional theory (DFT), developed recently by us, is employed to calculate hyperpolarizabilities of helium-like ions from their ground-state densities obtained from their respective Hylleraas wavefunctions. The only approximation made is that of the local density (LDA) for exchange and correlation. Use of densities — instead of wavefunctions — in density-based perturbation theory together with simple approximate energy functionals makes our calculations much simpler than those based on wavefunctions. They lead, however, to accurate results.     

Quantal density functional theory of excited states

We explain by quantal density functional theory the physics of mapping from any bound nondegenerate excited state of Schr?dinger theory to an S system of noninteracting fermions with equivalent density and energy. The S system may be in a ground or excited state. In either case, the highest occupied eigenvalue is the negative of the ionization potential. We demonstrate this physics with examples. The theory further provides a new framework for calculations of atomic excited states including multiplet structure.     

Hohenberg-Kohn theorem for the lowest-energy resonance of unbound systems

We show that under well-defined conditions the Hohenberg-Kohn theorem (HKT) that provides the foundation of ground-state density functional theory (DFT) can be extended to the lowest-energy resonance of unbound electronic systems. The extended version of the HKT provides an adequate framework to carry out DFT calculations of negative electron affinities.     

Static correlated functionals for reduced density matrix functional theory

Based on recent progress on fermionic exchange symmetry we propose a way to develop new functionals for reduced density matrix functional theory. For some settings with an odd number of electrons, by assuming saturation of the inequalities stemming from the generalized Pauli principle, the many-body wave-function can be written explicitly in terms of the natural occupation numbers and the natural orbitals. This leads to an expression for the two-particle reduced density matrix and therefore for the correlation energy functional. This functional is tested for a three-electron Hubbard model where it shows excellent performance both in the weak and strong correlation regimes.     

Nuclear energy density functionals constrained by low-energy QCD

A microscopic framework of nuclear energy density functionals is reviewed, which establishes a direct relation between low-energy QCD and nuclear structure, synthesizing effective field theory methods and principles of density functional theory. Guided by two closely related features of QCD in the low-energy limit: a) in-medium changes of vacuum condensates, and b) spontaneous breaking of chiral symmetry; a relativistic energy density functional is developed and applied in studies of ground-state properties of spherical and deformed nuclei.     

On the Problem of Universal Density Functional

A performed analysis shows that the density functional theory for the inhomogeneous electron gas, which is based on the hypothesis of the existence of the density functional for the external field potential is incorrect. This means that the density functional theory is not an ab initio theory.     

Derivation of the density functional theory from the cluster expansion

The density functional theory is derived from a cluster expansion by truncating the higher-order correlations in one and only one term in the kinetic energy. The formulation allows self-consistent calculation of the exchange correlation effect without imposing additional assumptions to generalize the local density approximation. The pair correlation is described as a two-body collision of bound-state electrons, and modifies the electron- electron interaction energy as well as the kinetic energy. The theory admits excited states, and has no self-interaction energy.     

Derivative discontinuities in density functional theory

Fifty years after the original formulation of density functional theory (DFT), subtle consequences of the mathematical mappings underlying its formalism continue to merit new views. In this article, we discuss the origin, the importance, and the challenges associated with finding the derivative discontinuity of the exchange-correlation (XC) energy of DFT at integer–electron numbers. We show how even the energy of a quantum electron gas with finite volume and number of electrons displays such derivative discontinuities, but continuous density functional approximations to the XC functional miss them entirely. We discuss some of the practical problems that arise due to this lack of derivative discontinuities in standard functionals, and explain new ways to recover them.     

Fluctuations in the level density of a fermi gas

We present a theory that accurately describes the counting of excited states of a noninteracting fermionic gas. At high excitation energies the results reproduce Bethe's theory. At low energies oscillatory corrections to the many-body density of states, related to shell effects, are obtained. The fluctuations depend nontrivially on energy and particle number. Universality and connections with Poisson statistics and random matrix theory are established for regular and chaotic single-particle motion.     

Kinetic energy of an inhomogeneous electron gas

It is well known that the kinetic energy of a system of N noninteracting particles in an external field V(r) in the nondegenerate ground state is a universal functional of the particle density (r) [1]. However, the explicit form of this functional is defined only for a certain class of functions (r). In particular, in the case of an almost constant or a slowly varying density we obtain the wellknown Thomas-Fermi-Weizsäcker-Kirzhnits functional [1, 2]. In [3] the kinetic energy functional of an electron in an atom is obtained in the WKB approximation. The kinetic energy of electrons with quantum numbers n andl is represented as the sum of two terms. The first term is written in the form of the density of the electrons with the given quantum numbers times some orthogonalized pseudopotential, which takes into account the orthogonality of their wave functions with respect to the core (its form is discussed below). The second term is the intrinsic kinetic energy of the electrons. The introduction of an orthogonalized pseudopotential is very convenient for the calculation of atomic properties [4, 5]. It is therefore of great interest to extend the results of [3] to the case of an electron gas in a metal and to obtain an expression for its orthogonalized crystalline pseudopotential. The solution of these problems is the aim of the present paper.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 7, pp. 117–120, July, 1977.     

Electrical response of molecular chains from density functional theory

The electrical response of molecular chains is dramatically overestimated by local and semilocal density functionals. We show that Kohn-Sham density-functional theory yields accurate linear and nonlinear polarizabilities when the exact exchange energy is employed together with the corresponding exact Kohn-Sham potential upsilonx(r). We further show that approximations to upsilonx(r) that are very accurate for the ground-state energy can nevertheless fail badly for the response because of potential barriers that have little effect on the ground-state energy but strongly affect the electron mobility.