Density functional. Theory and application to atoms and molecules

The density functional theory is one of the most efficient and promising methods of quantum physics and chemistry. It is a theory of electronic structure formulated in terms of the electron density as the basic unknown function instead of the electron wave function. According to the fundamental theorems of Hohenberg and Kohn, the electron density carries all the information one might need to determine any property of the electron system. However, the way of obtaining it, is not at all trivial. In this report, the recent advances are summarized. After a review of the Hohenberg–Kohn theorems, the method of constrained search and the Kohn–Sham scheme, exact theorems, relations and inequalities are discussed. There are several important concepts of chemistry (e.g. electronegativity, hardness, softness) that have recently obtained a firm foundation in the density functional theory. The optimized potential method and the methods that generate the potential from the electron density are reviewed. The local and nonlocal approximate functionals are compared. Extensions of the ground-state density functional theory (excited states, time-dependent, relativistic and finite temperature) are summarized. A review of the applications to atoms and molecules is presented.     

Reformulation of density functional theory for N-representable densities and the resolution of the v-representability problem

Density functional theory for the case of general, N-representable densities is reformulated in terms of density functional derivatives of expectation values of operators evaluated with wave functions leading to a density, making no reference to the concept of potential. The developments provide proof of existence of a mathematical procedure that determines whether a density is v-representable and in the case of an affirmative answer determines the potential (within an additive constant) as a derivative with respect to the density of a constrained search functional. It also establishes the existence of an energy functional of the density that, for v-representable densities, assumes its minimum value at the density describing the ground state of an interacting many-particle system. The theorems of Hohenberg and Kohn emerge as special cases of the formalism. Numerical results for one-dimensional non-interacting systems illustrate the formalism. Some direct formal and practical implications of the present reformulation of DFT are also discussed.     

Analysis of multi-configuration density functional theory methods: theory and model application to bond-breaking

We consider the extension of the standard single-determinant Kohn–Sham method to the case of a multi-configuration auxiliary wave function. By applying the rigorous Kohn–Sham method to this case, we construct the proper interacting and auxiliary energy functionals. Following the Hohenberg–Kohn theorem for both energy functionals, we derive the corresponding multi-configuration Kohn–Sham equations, based on a local effective potential. At the end of the analysis we show that, at the ground state, the auxiliary wavefunction must collapse into a single-determinant wave function, equal to the regular KS wavefunction. We also discuss the stability of the wavefunction in multi-configuration density functional theory methods where the auxiliary system is partially interacting, and the remaining (residual) correlation is evaluated as a functional of the density. As an example showing both the challenges and the possibilities, we implement such a procedure for the perfect pairing wavefunction, using a residual correlation functional that is based on the Lee–Yang–Parr functional, and present results for an elementary bond-breaking process.     

Ground state of an impurity in a homogeneous system in the hypernetted chain approximation

The hypernetted chain theory of the ground state of a homogeneous N-particle medium NM with an impurity particle is presented. The N identical particles are fermions with spin-isospin degeneracy ν, or bosons (in the limit of ν → ∞). The ground-state wave-function of the system is assumed in the Jastrow form with central, state-independent correlation functions. Central, spin-isospin-dependent two-body interactions both in NM and between the impurity particle and the particles of NM are considered. Expressions for the ground-state energy of the system and for the separation energy of the impurity particle are derived. The simplified case of the chain approximation is also considered.     

Microscopic calculation of a model 16O nucleus

We present variational calculations for a hypothetical system of 16 nucleons interacting via the Malfliet-Tjon potential and compare our results with the Green-function Monte Carlo (GFMC) data of Helmbrecht et al.For a system of 16 bosons, we find that the (approximate) ground-state energy of our optimized hypernetted-chain calculation agrees with the GFMC data within 1%. For fermions, we find that the optimized Fermi hypernetted chain calculation leads to a ground state energy between the GFMC data and the variational Monte Carlo result with non-optimized correlations; the one-body density predicted by the FHNC theory agrees well with the one predicted by the GFMC calculation.     

On the Q-condition for fermion N-representability

It is shown that if a 2-particle fermion density operator satisfies the Q-condition for N-representability, then its 1-particle contraction is N-representable. This is an extension of Coleman's theorem to the infinite rank case.     

Absence of proof for the Hohenberg–Kohn theorem for a Hamiltonian linear in the magnetic field

ABSTRACT

The widespread idea that spin-density functional theory is based upon the extension of the Hohenberg–Kohn theorem to weak magnetic fields is contested. First, it is assumed that only the term linear in magnetic field can be kept in the Hamiltonian. Second, once this is done, two problems arise (1) not only the spin-dependent, but also the orbital-dependent term should be taken care of, and (2) the latter produces eigenvalues that are not bounded from below, thus invalidating the proof of the Hohenberg–Kohn theorem.     

Spin-correlations and low lying excited states of the spin-1/2 Heisenberg antiferromagnet on a square lattice

The ground state and the lowest excited states of the spin 1/2-Heisenberg model are investigated by exact diagonalization and variational Monte Carlo techniques. Our trial state represents a generalization of a wave function introduced by Hulthen, Kasteleijn and Marshall. The long range character of the spin-correlation function is in excellent agreement with exact diagonalization and also with recent neutron scattering results for La₂CuO₄. The asymptotic behavior of the spin-correlation function is found to differ from spin-wave theory. From the exact (N<=20 spins) and variational (N<=400) ground state energies we determine as asymptotic values 1.3025 and 1.288, respectively. We calculate the dispersion for the spin-wave excitations and identify an excited triplet which becomes degenerate with the ground state in the thermodynamic limit. This triplet state allows spontaneous symmetry breaking to occur atT=0 K. Quantum fluctuations reduce the sublattice magnetization to an effective value of 0.195 (3) as compared to the Néel-state value of 1/2.     

Decays of 2++ mesons into Goldstone Fermions

We discuss the decay of 2⁺⁺ mesons into two Goldstone Fermions λ arising in a recently proposed model whereN=1 supersymmetry is realized in a nonlinear way. Some bounds on the coupling constant of the λ-particle are given.     

N-particle Bogoliubov vacuum state

We consider the Bogoliubov vacuum state in the number-conserving Bogoliubov theory proposed by Castin and Dum [Phys. Rev. A 57, 3008 (1998)]. We show that, in the particle representation, the vacuum can be written in a simple diagonal form. The vacuum state can describe the stationary N-particle ground state of a condensate in a trap, but it can also represent a dynamical state when, for example, a Bose-Einstein condensate initially prepared in the stationary ground state is subject to a time-dependent perturbation. In both cases the diagonal form of the Bogoliubov vacuum can be obtained by basically diagonalizing the reduced single-particle density matrix of the vacuum. We compare N-body states obtained within the Bogoliubov theory with the exact ground states in a 3-site Bose-Hubbard model. In this example, the Bogoliubov theory fails to accurately describe the stationary ground state in the limit when N → ∞ but a small fraction of depleted particles is kept constant.     

Impurity contribution to the specific heat in the Kondo model

Summary Using the Lanczos scheme (tridiagonalization) we investigate the impurity contribution to the single-impurity Kondo model. This is accomplished by obtaining the ground-state energy of aN-particle system and a (N+1)-particle system, and obtaining the functional dependence ofg(J) (whereJ is the strength of the interaction). Hereg(J) is the coefficient of a correction term which is of order 1/N. The density of states at the Fermi level is effectively changed by the factorg(J). The excess heat capacity associated with the impurity is then proportional tog(J). To speed up publication, the authors of this papers have agreed to not receive the proofs for correction.     

The complex Kohn variational method applied to N-d scattering

The three-nucleon ground state and the N-d scattering states are obtained using variational principles. The wave function of the system is decomposed into angular-spin-isospin channels and the corresponding two dimensional spatial amplitudes are expanded in a correlated polynomial basis. For the scattering states, the complex form of the Kohn variational principle is used to determine the S-matrix. Special attention is given to the convergence pattern of the phase-shift and mixing parameters. The calculations have been performed using realistic local NN potentials and three-nucleon forces. Important features of the method are anomaly-free solutions and the low dimensionality of the matrices involved allowing for the inclusion of a large number of states. Very precise and stable numerical results have been obtained.     

Rigidity of the Laughlin Liquid

We consider general N-particle wave functions that have the form of a product of the Laughlin state with filling factor \(1/\ell \) and an analytic function of the N variables. This is the most general form of a wave function that can arise through a perturbation of the Laughlin state by external potentials or impurities, while staying in the lowest Landau level and maintaining the strong correlations of the original state. We show that the perturbation can only shift or lower the 1-particle density but nowhere increase it above a maximum value. Consequences of this bound for the response of the Laughlin state to external fields are discussed.     

Influence of excited Landau levels on a two-dimensional electron-hole system in a strong perpendicular magnetic field

The study of the quantum states of a two-dimensional electron-hole system in a strong perpendicular magnetic field is carried out with special attention to the influence of virtual quantum transitions of interacting particles between the Landau levels. These virtual quantum transitions from the lowest Landau levels to excited Landau levels with arbitrary quantum numbers n and m and their reversion to the lowest Landau levels in second order perturbation theory result in an indirect attraction between the particles. The influence of the indirect interaction on the magnetoexciton ground state, on the chemical potential of the Bose-Einstein condensed magnetoexcitons, and on the ground state energy of the metallic-type electron-hole liquid is investigated in the Hartree-Fock approximation. The coexistence of different phases is suggested.     

Collective electronically excited states of a uniform chain of atoms

Electronically excited states of finite uniform chains of atoms were considered taking into account the influence of the continuous energy spectrum. Traditional quantum-chemical methods for calculating two-electron transitions between neighboring chain atoms were combined with the asymptotic theory of interactions between excited atoms and neutral particles and the mathematical apparatus of the theory of multiple scattering for taking into account intercenter transitions in an ensemble of interacting centers. Recurrence equations for describing energy zones containing symmetrical and antisymmetric excited state levels of chains with an arbitrary length were obtained. Depending on system parameters, different modes of the distribution of the electron density of collective excited states were possible. At a certain ratio between level shifts and exchange integral values, excited states with a uniform electron density distribution over all chain nodes could form for certain solutions. This was a fortuitous circumstance caused by the influence of the continuous spectrum. Such states appeared at small principal quantum number n values, they were similar to one-electron excitations of the type of Frenkel excitons, when an electron was localized near its Coulomb center. These conditions were rapidly disturbed as n increased, and one-electron excitations of a linear molecule were formed in the system (that is, limiting excitations of the type of Wannier-Mott excitons did not form).     

Reduced density matrices of a system of N coupled oscillators 2. eigenstructure of the 1-particle matrix for the canonical ensemble

The following theorem is proved: The reduced 1-particle density matrix corresponding to an equilibrium state of a system of N coupled oscillators coincides with the density matrix of a canonical ensemble of free oscillators at some effective temperature.     

Correlations in the ground state of the one-dimensional Hubbard model

With eigenfunctional theory and a rigorous expression of exchange-correlation energy of a general interacting electron system, we study the ground state properties of the one-dimensional Hubbard model, and calculate the ground-state energy as well as the charge gap at half-filling for arbitrary coupling strength u=U/(4t) and electron density nc. We find that the simple linear approximation of the phase field works well in weak coupling case, but it becomes inappropriate as the on-site Coulomb interaction becomes strong where the fluctuations of the bosonic auxiliary field are strong. Then we propose a new scheme by adding Gutzwiller projection which suppresses the density fluctuations and the new results are quite close to the exact ones up to considerably strong coupling strength u=3.0 and for arbitrary electron density nc. Our calculation scheme is proved to be effective for strongly correlated electron systems in one dimension, and its extension to higher dimensions is straightforward.     

A Note on the Eigenvalue Density of Random Matrices

The distribution of eigenvalues of N 2 N random matrices in the limit N M X is the solution to a variational principle that determines the ground state energy of a confined fluid of classical unit charges. This fact is a consequence of a more general theorem, proven here, in the statistical mechanics of unstable interactions. Our result establishes the eigenvalue density of some ensembles of random matrices which were not covered by previous theorems.     

Renormalized proton- neutron QRPA and double beta decay of 82Se to excited states in 82Kr

We apply the self-consistent renormalized proton-neutron QRPA (RQRPA) method to calculate the two-neutrino double beta (2νββ) decay matrix elements associated with the ground-state and excited-state transitions of the ⁸²Se → ⁸²Kr decay. The RQRPA method is an extension of the pnQRPA method and promotes the Pauli exclusion principle violated by the pnQRPA ground state and yields more stable nuclear matrix elements with increasing strength of the proton-neutron interaction. In the present work the RQRPA wave functions are also used to evaluate 2νββ-decay rates to excited final states. The resulting theoretical half lives are compared with the new stringent experimental limits obtained by using a HPGe detector and external sources of enriched selenium.