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The Journal of Chemical Physics

Long-range asymptotic behavior of ground-state wave functions, one-matrices, and pair densities

Matthias Ernzerhof, Kieron Burke, John P. Perdew

Published Aug 15, 1996• 58 citations
Publisher

Abstract

The asymptotic behavior of an N-electron ground-state wave function is analyzed, as one electron wanders far from the system. Implications for the one-matrix and pair density are described. The asymptotic behavior currently discussed in the literature, in which the remaining (N−1) electrons relax to their ground state, is generalized to the case where the (N−1)-electron ground state is degenerate. Infinitely long-ranged correlations are reported, in which the selected (N−1)-electron ground state depends upon the direction along which one electron wandered off. We correct a standard limit for the one matrix. Numerical and analytic studies of accurate correlated wave functions illustrate and support the standard asymptotic behavior for the nondegenerate case and its generalization derived here. We extract the (N−1)-electron density from the correlated N-electron wave function. We also discuss the question how large the separation of one electron must be to realize the limiting behavior.

DOI
10.1063/1.472142

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The asymptotic behavior of an N-electron ground-state wave function is analyzed, as one electron wanders far from the system. Implications for the one-matrix and pair density are described. The asymptotic behavior currently discussed in the literature, in which the remaining (N−1) electrons relax to their ground state, is generalized to the case where the (N−1)-electron ground state is degenerate. Infinitely long-ranged correlations are reported, in which the selected (N−1)-electron ground state depends upon the direction along which one electron wandered off. We correct a standard limit for the one matrix. Numerical and analytic studies of accurate correlated wave functions illustrate and support the standard asymptotic behavior for the nondegenerate case and its generalization derived here. We extract the (N−1)-electron density from the correlated N-electron wave function. We also discuss the question how large the separation of one electron must be to realize the limiting behavior.
We consider the one-dimensional spinless Falicov-Kimball model of itinerant fermionic particles (``spinless electrons''), which can hop between nearest-neighbour sites only, and of immobile particles (``classical ions''), with an on-site attraction. Extensive studies of the ground-state phase diagram of this system and its higher dimensional counterparts, carried out up to now, concentrated on determining ground-state arrangements of ions on the underlying lattice, while the properties of electrons were typically ignored. We report studies of short- and long-range correlations between electrons, and between ions and electrons, and of the spatial decay of electron correlations (decay of single-particle density matrix), in the ground state. The studies have been carried out analytically and by means of well-controlled numerical procedures. In the case of period 2 ground state, the single-particle density matrix has been expressed in terms of a hypergeometric function, and its spatial decay has been extracted. Numerical calculations have been done for open chains of various lengths (up to a few thousand sites), in order to control the chain-size dependence of correlations and to extrapolate the results to the limit of infinite chain. A part of the obtained results refers to tight-binding electrons subjected to a periodic external potential due to the ions, which constitute simple models of metals and insulators.
A formulation is proposed to treat the ground-state properties of an assembly of electrons, interacting mutually through the Coulomb potential and confined by an external potential V whose maximum is finite so that both bound and extended continuum states appear as eigen states for the one-body Hamiltonian composed of the electron kinetic energy and V . These extended states are found to play a crucial role in incorporating the effect of electron correlation into the localized ground-state many-electron wave function. As an illustration of our formalism, the ground-state energy of a He atom is calculated in its simplest version and compared rather successfully with experiment as well as the results in other serious numerical methods. We also calculate the density and pair distribution functions in the same version. Special attention is paid to the latter function in this system in order to elucidate a qualitative difference from that in the homogeneous electron gas. This function shows clearly that the two electrons with opposite spins in He correlate strongly over quite a long range in contrast to the common expectation that the ground-state wave function for the He atom can be described accurately in the Hartree-Fock approximation.
Strong electron correlation in materials is explored within a class of model Hamiltonians that treat only pair interactions between electrons. The model is unique among typical spin Hamiltonians in that it does not have an effective mean-field reference wave function. The ground-state wave functions from all Hamiltonians in the model have the same one-electron reduced density matrix (1-RDM); consequently, one-electron theories such as the Hartree–Fock and density functional theories are inapplicable. In contrast, the ground-state two-electron reduced density matrix (2-RDM) has a one-to-one mapping to the ground-state wave function. For a range of lattices including linear, ladder, and square topologies, we variationally compute the 2-RDM subject to constraints, known as N -representability conditions, that are necessary for the 2-RDM to represent an N -electron ensemble density matrix. We find that for all model Hamiltonians the 2-RDM is accurately computed as long as the D, Q, and G N -representability conditions are supplemented with the T 2 condition. Energies, orbital and geminal occupation numbers, and correlation functions are computed. The model has applications to superconductivity as well as more general pairing phenomena in electronic systems. Effective methods are needed to treat strong electron correlation arising in the study of materials including the study of high-temperature superconductivity and phase transitions.
The behavior of long space-time excitations in many-electron systems with ground state degeneracy is explored via multiscale analysis. The analysis starts with an ansatz for the wave function's dual dependence on the N-electron configuration (i.e., both by direct means and by indirect means via a set of order parameters). It is shown that a Dirac-like equation form of the wave equation emerges in the limit where the ratio epsilon (of the average nearest-neighbor distance to the characteristic length of the long-scale phenomenon of interest) is small. Examples of the long scale are the size of a quantum dot, nanotube, or wavelength of a density disturbance. The velocities in the Dirac-like equation are the transition moments of the single-particle momentum operator connecting degenerate ground states. While detailed band structure and the independent quasi-particle picture could underlie the behavior of some systems (as commonly suggested for graphene), the present scaling law results show it is not necessarily the only explanation. Rather, it can follow from the scaling properties of low-lying, long spatial scale excitations and ground state degeneracy, even in strongly interacting systems. The generality of our findings suggests graphene may be just one of many examples of Dirac-like equation behavior. A preliminary validation of our quantum scaling law for molecular arrays is presented. As our scaling law constitutes a coarse-grained wave equation, path integral or other methods derived from it hold great promise for calibration-free, long-time simulation of many-particle quantum systems.
Explicit asymptotic expressions are derived for the reduced one-electron density matrices (the 1-matrices) of strongly correlated two- and three-electron harmonium atoms in the ground and first excited states. These expressions, which are valid at the limit of small confinement strength ω, yield electron densities and kinetic energies in agreement with the published values. In addition, they reveal the ω(5/6) asymptotic scaling of the exchange components of the electron-electron repulsion energies that differs from the ω(2/3) scaling of their Coulomb and correlation counterparts. The natural orbitals of the totally symmetric ground state of the two-electron harmonium atom are found to possess collective occupancies that follow a mixed power/Gaussian dependence on the angular momentum in variance with the simple power-law prediction of Hill's asymptotics. Providing rigorous constraints on energies as functionals of 1-matrices, these results are expected to facilitate development of approximate implementations of the density matrix functional theory and ensure their proper description of strongly correlated systems.
We propose a method that employs functionals of the one-electron reduced density matrix (density matrix) to capture long-range effects of electron correlation. The complementary short-range regime is treated with density functionals. In an effort to find approximations for the long-range density-matrix functional, a modified power functional is applied to the homogeneous electron gas with Coulomb interactions replaced by their corresponding long-range counterparts. For the power $\ensuremath{\beta}=1/2$ and the range-separation parameter $\ensuremath{\omega}=1/{r}_{s}$, the functional reproduces the correlation and the kinetic correlation energies with a remarkable accuracy for intermediate and large values of rs{r}_{s}rs​. Analysis of the Euler equation corresponding to this functional reveals correct rs{r}_{s}rs​ expansion of the correlation energy in the limit of large rs{r}_{s}rs​. The first expansion coefficient is in very good agreement with that obtained from the modified Wigner-Seitz model.