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The Journal of Chemical Physics

Natural occupation numbers in two-electron quantum rings

Vincent Tognetti, Pierre‐François Loos

Published Feb 5, 2016• 11 citations
Publisher

Abstract

Natural orbitals (NOs) are central constituents for evaluating correlation energies through efficient approximations. Here, we report the closed-form expression of the NOs of two-electron quantum rings, which are prototypical finite-extension systems and new starting points for the development of exchange-correlation functionals in density functional theory. We also show that the natural occupation numbers for these two-electron paradigms are in general non-vanishing and follow the same power law decay as atomic and molecular two-electron systems.

DOI
10.1063/1.4940919

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Natural orbitals (NOs) are central constituents for evaluating correlation energies through efficient approximations. Here, we report the closed-form expression of the NOs of two-electron quantum rings, which are prototypical finite-extension systems and new starting points for the development of exchange-correlation functionals in density functional theory. We also show that the natural occupation numbers for these two-electron paradigms are in general non-vanishing and follow the same power law decay as atomic and molecular two-electron systems.
Previously unknown properties of the natural orbitals (NOs) pertaining to singlet states (with natural parity, if present) of electronic systems with even numbers of electrons are revealed upon the demonstration that, at the limit of n → ∞, the NO ψ n ( r⃗ ) with the n th largest occupation number ν n approaches the solution ψ̃ n ( r⃗ ) of the zero-energy Schrödinger equation that reads T̂ ([ ρ 2 ( r⃗, r⃗ )] −1/8 ψ̃ n (r⃗)) − (π 2 / ṽ n ) 1/4 [ρ 2 ( r⃗, r⃗ )] 1/4 ([ρ 2 ( r⃗, r⃗ )] −1/8 ψ̃ n (r⃗)) = 0 (where T̂ is the kinetic energy operator), whereas ν n approaches ν̃ n . The resulting formalism, in which the “on-top” two-electron density ρ 2 ( r⃗, r⃗ ) solely controls the asymptotic behavior of both ψ n ( r⃗ ) and ν n at the limit of the latter becoming infinitesimally small, produces surprisingly accurate values of both quantities even for small n . It opens entirely new vistas in the elucidation of their properties, including single-line derivations of the power laws governing the asymptotic decays of ν n and ⟨ψ n ( r⃗ )| T̂ |ψ n ( r⃗ )⟩ with n, some of which have been obtained previously with tedious algebra and arcane mathematical arguments. These laws imply a very unfavorable asymptotics of the truncation error in the total energy computed with finite numbers of natural orbitals that severely affects the accuracy of certain quantum-chemical approaches such as the density matrix functional theory. The new formalism is also shown to provide a complete and accurate elucidation of both the observed order (according to decreasing magnitudes of the respective occupation numbers) and the shapes of the natural orbitals pertaining to the 1 Σ g + ground state of the H 2 molecule. In light of these examples of its versatility, the above Schrödinger equation is expected to have its predictive and interpretive powers harnessed in many facets of the electronic structure theory.
The non-vanishing of the natural orbital (NO) occupation numbers of the one-particle density matrix of many-body systems has important consequences for the existence of a density matrix-potential mapping for nonlocal potentials in reduced density matrix functional theory and for the validity of the extended Koopmans' theorem. On the basis of Weyl's theorem we give a connection between the differentiability properties of the ground state wavefunction and the rate at which the natural occupations approach zero when ordered as a descending series. We show, in particular, that the presence of a Coulomb cusp in the wavefunction leads, in general, to a power law decay of the natural occupations, whereas infinitely differentiable wavefunctions typically have natural occupations that decay exponentially. We analyze for a number of explicit examples of two-particle systems that in case the wavefunction is non-analytic at its spatial diagonal (for instance, due to the presence of a Coulomb cusp) the natural orbital occupations are non-vanishing. We further derive a more general criterium for the non-vanishing of NO occupations for two-particle wavefunctions with a certain separability structure. On the basis of this criterium we show that for a two-particle system of harmonically confined electrons with a Coulombic interaction (the so-called Hookium) the natural orbital occupations never vanish.
We introduce a novel energy functional for ground-state electronic-structure calculations. Its fundamental variables are the natural spin-orbitals of the implied singlet many-body wave function and their joint occupation probabilities. The functional derives from a sequence of controlled approximations to the two-particle density matrix. Algebraic scaling of computational cost with electron number is obtainable in general, and Hartree-Fock scaling in the seniority-zero version of the theory. Results obtained with the latter version for saturated small molecular systems are compared with those of highly-accurate quantum-chemical computations. The numerical results are variational, capturing most of the correlation energy from equilibrium to dissociation. Their accuracy is considerably greater than that obtainable with current density-functional theory approximations and with current functionals of the one-particle density matrix only.
We introduce an energy functional for ground-state electronic structure calculations. Its variables are the natural spin-orbitals of singlet many-body wave functions and their joint occupation probabilities deriving from controlled approximations to the two-particle density matrix that yield algebraic scaling in general, and Hartree-Fock scaling in its seniority-zero version. Results from the latter version for small molecular systems are compared with those of highly accurate quantum-chemical computations. The energies lie above full configuration interaction calculations, close to doubly occupied configuration interaction calculations. Their accuracy is considerably greater than that obtained from current density-functional theory approximations and from current functionals of the one-particle density matrix.
Occupation numbers of natural orbitals capture the physics of strong electron correlations in momentum space. A natural orbital density functional theory based on the antisymmetrized geminal product provides these occupation numbers and the corresponding electron momentum density. A practical implementation of this theory approximates the natural orbitals by the Kohn–Sham orbitals and uses a mean-field approach to estimate pairing amplitudes leading to corrections for the independent particle model. The method is applied to weakly doped La2CuO4.
Abstract Density functional theory (DFT) is usually formulated in terms of the electron density as a function of position n(r). Here we discuss an alternative formulation of DFT in terms of the orbital occupation numbers {n α } associated with a local-orbital orthonormal basis set {ϕ α }. First, we discuss how the building blocks of DFT, namely the Hohenberg–Kohn theorems, the Levy–Lieb approach and the Kohn–Sham method, can be adapted for a description in terms of {n α }. In particular, the total energy is now a function of {n α }, E[{n α }], and a Kohn–Sham-like Hamiltonian is derived introducing the effects of the electron–electron interactions via effective potentials, { V α eff = ∂ E e e [ { n β } ] / ∂ n α } . In a second step we consider the Hartree and exchange energies and discuss how to describe them, in the spirit of a DFT approach, in terms of the orbital occupation numbers. In this contribution special attention is paid to the description of the (intra-atomic) correlation energy and corresponding correlation potentials {V corr,α }. For this purpose, a model system is analyzed in detail, whereby an atomic Hamiltonian interacts with the environment via a simplified model; the use of this model allows us to obtain the correlation energy and potentials (in terms of {n α }) for different cases corresponding to low, intermediate and high electron correlations.