Significance The ground state of a quantum mechanical system is the lowest-energy eigenstate of the Hamiltonian. In isolation, it persists unchanged forever, with symmetries dictated by those of the Hamiltonian. But near-eigenstates of broken symmetry can persist for long times, even on the scale of human measurement. The appearance of broken symmetries of the electron density or spin density in a density functional calculation can reveal strong correlations among the electrons that are present in a symmetry-unbroken wavefunction. Symmetry breaking can arise when a wave-like fluctuation drops to zero frequency. The presented examples are the stretched hydrogen molecule, antiferromagnetism in solids, and the static charge-density wave in a low-density jellium, which is shown quantitatively to be a zero-frequency plasma wave.
Significance The ground state of a quantum mechanical system is the lowest-energy eigenstate of the Hamiltonian. In isolation, it persists unchanged forever, with symmetries dictated by those of the Hamiltonian. But near-eigenstates of broken symmetry can persist for long times, even on the scale of human measurement. The appearance of broken symmetries of the electron density or spin density in a density functional calculation can reveal strong correlations among the electrons that are present in a symmetry-unbroken wavefunction. Symmetry breaking can arise when a wave-like fluctuation drops to zero frequency. The presented examples are the stretched hydrogen molecule, antiferromagnetism in solids, and the static charge-density wave in a low-density jellium, which is shown quantitatively to be a zero-frequency plasma wave.
In the widely-used Kohn-Sham density functional theory for the manyelectron ground state, only the density functional for the exchange-correlation energy is approximated. While the exact density functional minimizes at the exact ground-state energy for any system, widely used approximations can at best describe normally-correlated ground states. A “proper” approximation for a given problem is defined as one that well describes relevant normally-correlated states. Strong correlation, present in many quantum materials, can arise due to abnormally high degeneracy of the Kohn-Sham occupied and unoccupied one-electron energies near the Fermi level. In such situations, the approximate functional may lower its energy by spontaneously breaking symmetries that the ground-state density shares with the many-electron Hamiltonian, reducing the degeneracies that lead to strong correlation. Here the Levy constrained search is invoked to argue that the total energy of a “proper” functional with maximal spontaneous symmetry breaking is bounded from below by the exact total energy, and that the bound may be close to the extent that the abnormal degeneracies are removed. This is a consequence of a variational principle, and it may not hold in non-variational but more accurate approaches to normal correlation such as coupled cluster theory. Since the correlation energy of any one-electron state is zero, a widely “proper” approximate functional should be nearly or exactly self-interaction free, and progress toward a proper self-interaction correction is reviewed here. The time-centered physical interpretation of symmetry breaking is also discussed.
We consider a quantum many-body system on a lattice which exhibits a spontaneous symmetry breaking in its infinite volume ground states, but in which the corresponding order operator does not commute with the Hamiltonian. Typical examples are the Heisenberg antiferromagnet with a Néel order, and the Hubbard model with a (superconducting) off-diagonal long range order. In the corresponding finite system, the symmetry breaking is usually “obscured ” by “quantum fluctuation ” and one gets a symmetric ground state with a long range order. In such a situation, Horsch and von der Linden proved that the finite system has a low-lying eigenstate whose excitation energy is not more than of order N −1, where N denotes the number of the sites in the lattice. Here we study the situation where the broken symmetry is a continuous one. For a particular set of states (which are orthogonal to the ground state and with each other), we prove bounds for their energy expectation values. The bounds establish that there exist ever increasing numbers of low-lying eigenstates whose excitation energies are bounded by a constant times N −1. A crucial feature of the particular low-lying
The quantum mechanics of two-electron systems is reviewed, starting with the ground state of the helium atom and heliumlike ions with central charge Z. The case of Z≥2 is rather straightforward. In contrast, for negative hydrogen ion with Z=1, the stability of H− cannot be achieved using a product of individual electron wavefunctions and requires explicit account of the anticorrelation among the two electrons. The wavefunction proposed by Chandrasekhar is revisited, where the permutation symmetry is first broken and then restored by a counterterm. More difficult problems can be studied using the same strategy such as the stability of hydrogenlike ions for any value of the proton-to-electron mass ratio M/m, the energy of the lowest spin-triplet state of helium and heliumlike ions, and the stability of the doubly excited hydrogen ion with unnatural parity. The positronium molecule, which was predicted years ago and discovered recently, can also be shown to be stable against spontaneous dissociation. Emphasis is placed on symmetry breaking, which can either spoil or improve the stability.
Material scientists and condensed matter physicists have long been divided on the issue of choosing the conceptual framework for explaining why open-shell transition-metal oxides tend to be insulators, whereas otherwise successful theories such as DFT often predict them to be (false) metals. Strong correlation becomes the recommended medicine. We point out that strong correlation can be mitigated by allowing DFT to lower the energy by breaking structural, magnetic or dipolar symmetries. Such local motifs are observed experimentally by local probes beyond the 'average structure' determined by X-Ray diffraction. Observed broken symmetries can arise from slow fluctuations that persist over the observation time or longer. The surprising fact is that when symmetry breaking motifs are used as input to electronic structure calculations, false metals are converted into real insulators without the recommended medicine of strong correlation. Consistently, DFT calculations that show energy lowering symmetry breaking correct most cases where DFT, even with advanced exchange-correlation functionals, previously missed the correct metal vs insulator designation. Total energy calculations distinguish systems that support energy-lowering symmetry breaking from those that do not. This approach distinguishes between paramagnetic insulating and metallic phases and shows mass enhancement in Mott metals. The reason is that symmetry breaking removes many of the degeneracies that exist in a symmetry-unbroken system, reducing significantly the need for strong correlation. If one chooses to ignore symmetry breaking, the persistent degeneracies often call for strong correlation treatment. Thus, symmetry breaking transforms strong to normal correlation and false metals to true insulators. This view sheds light on the historic controversy between Mott and Slater that still reverberates today.
In this work, we explore the performance of approximations to electron correlation in reduced density-matrix functional theory (RDMFT) and of approximations to the observables calculated within this theory. Our analysis focuses on the calculation of total energies, occupation numbers, removal/addition energies, and spectral functions. We use the exactly solvable Hubbard dimer at 1/4 and 1/2 fillings as test systems. This allows us to analyze the underlying physics and to elucidate the origin of the observed trends. For comparison, we also report the results of the GW approximation, where the self-energy functional is approximated, but no further hypothesis is made concerning the approximations of the observables. In particular, we focus on the atomic limit, where the two sites of the dimer are pulled apart and electrons localize on either site with equal probability, unless a small perturbation is present: this is the regime of strong electron correlation. In this limit, using the Hubbard dimer at 1/2 filling with or without a spin-symmetry-broken ground state allows us to explore how degeneracies and spin-symmetry breaking are treated in RDMFT. We find that, within the used approximations, neither in RDMFT nor in GW, the signature of strong correlation is present, when looking at the removal/addition energies and spectral function from the spin-singlet ground state, whereas both give the exact result for the spin-symmetry broken case. Moreover, we show how the spectroscopic properties change from one spin structure to the other.
Abstract Symmetry-breaking phases in many-fermion systems are characterized by anomalous functions that describe transient processes in which certain properties of free particles, such as spin or charge, are not conserved. Connecting the low-temperature symmetry-breaking phase with the high-temperature phase within the Baym-Kadanoff scheme, beyond the static mean-field approximation, remains a long-standing challenge. We identify the reason why approximations that include critical dynamical fluctuations in the Schwinger-Dyson equation yield mismatched transition temperatures between the high- and low-temperature phases. We find a solution to this generic problem and show that the mismatch in closed systems arises from the inappropriate inclusion of anomalous contributions to the free electron-hole propagator that fail to maintain the balance between the incoming and outgoing excited states. We illustrate this behavior with an antiferromagnetic state calculated in the FLEX approximation. We find a two-gap structure in the spectral function in the antiferromagnetic phase when strong electron correlations are present.