The concept of correlation is central to all approaches that attempt the description of many-body effects in electronic systems. Multipartite correlation is a quantum information theoretical property that is attributed to quantum states independent of the underlying physics. In quantum chemistry, however, the correlation energy (the energy not seized by the Hartree-Fock ansatz) plays a more prominent role. We show that these two different viewpoints on electron correlation are closely related. The key ingredient turns out to be the energy gap within the symmetry-adapted subspace. We then use a few-site Hubbard model and the stretched ${\mathrm{H}}_{2}$ to illustrate this connection and to show how the corresponding measures of correlation compare.
The concept of correlation is central to all approaches that attempt the description of many-body effects in electronic systems. Multipartite correlation is a quantum information theoretical property that is attributed to quantum states independent of the underlying physics. In quantum chemistry, however, the correlation energy (the energy not seized by the Hartree-Fock ansatz) plays a more prominent role. We show that these two different viewpoints on electron correlation are closely related. The key ingredient turns out to be the energy gap within the symmetry-adapted subspace. We then use a few-site Hubbard model and the stretched H2 to illustrate this connection and to show how the corresponding measures of correlation compare.
We use the concept of quantum entanglement to give a physical meaning to the electron correlation energy in systems of interacting electrons. The electron correlation is not directly observable, being defined as the difference between the exact ground state energy of the many-electron Schr ̈odinger equation and the Hartree–Fock energy. Using the configuration interaction method for the hydrogen molecule, we calculate the correlation energy and compare it with the entanglement as a function of the nucleus– nucleus separation. In the same spirit, we analyze a dimer of ethylene, which represents the simplest organic conjugate system, changing the relative orientation and distance of the molecules to obtain the configuration corresponding to maximum entanglement.
This review explains the relationship between density functional theory and strongly correlated models using the simplest possible example, the two-site Hubbard model. The relationship to traditional quantum chemistry is included. Even in this elementary example, where the exact ground-state energy and site occupations can be found analytically, there is much to be explained in terms of the underlying logic and aims of Density Functional Theory. Although the usual solution is analytic, the density functional is given only implicitly. We overcome this difficulty using the Levy-Lieb construction to create a parametrization of the exact function with negligible errors. The symmetric case is most commonly studied, but we find a rich variation in behavior by including asymmetry, as strong correlation physics vies with charge-transfer effects. We explore the behavior of the gap and the many-body Green’s function, demonstrating the ‘failure ’ of the Kohn-Sham method to reproduce the fundamental gap. We perform benchmark calculations of the occupation and components of the KS potentials, the correlation kinetic energies, and the adiabatic connection. We test several approximate functionals (restricted and unrestricted Hartree-Fock and Bethe Ansatz Local Density Approximation) to show their successes and limitations. We also discuss and illustrate the concept of the derivative discontinuity. Useful appendices include analytic expressions for Density
This review explains the relationship between density functional theory and strongly correlated models using the simplest possible example, the two-site Hubbard model. The relationship to traditional quantum chemistry is included. Even in this elementary example, where the exact ground-state energy and site occupations can be found analytically, there is much to be explained in terms of the underlying logic and aims of density functional theory. Although the usual solution is analytic, the density functional is given only implicitly. We overcome this difficulty using the Levy-Lieb construction to create a parametrization of the exact function with negligible errors. The symmetric case is most commonly studied, but we find a rich variation in behavior by including asymmetry, as strong correlation physics vies with charge-transfer effects. We explore the behavior of the gap and the many-body Green's function, demonstrating the 'failure' of the Kohn-Sham (KS) method to reproduce the fundamental gap. We perform benchmark calculations of the occupation and components of the KS potentials, the correlation kinetic energies, and the adiabatic connection. We test several approximate functionals (restricted and unrestricted Hartree-Fock and Bethe ansatz local density approximation) to show their successes and limitations. We also discuss and illustrate the concept of the derivative discontinuity. Useful appendices include analytic expressions for density functional energy components, several limits of the exact functional (weak- and strong-coupling, symmetric and asymmetric), various adiabatic connection results, proofs of exact conditions for this model, and the origin of the Hubbard model from a minimal basis model for stretched H2.
The gate and qubit requirements of quantum computations of electronic structure have been extensively studied. However, the quantum resources present in electronic ground states, as measured by entanglement and magic, remain less well understood. We study the relationship between correlation in electronic structure Hamiltonians and magic as measured by the 2-stabilizer Renyi entropy (2-SRE). Perturbative calculations show that the 2-SRE of a given state is proportional to its overlap with a reference stabilizer state. In the context of quantum chemistry, this links the magic of electronic structure ground states to their Hartree-Fock weight, an established measure of electronic correlation. We then show that the 2-SRE of post-Hartree-Fock ground states is proportional to the correlation energy they recover. We explore this connection through the contextual subspace (CS) method. We present a theoretical framework showing that the CS method can be used to monotonically vary the magic of approximate CS ground states, and we prove that the correlation energy recovered by the CS ground states is proportional to the magic present in the approximate ground state. We present simulation results using 190 molecular species under Jordan-Wigner encoding at a range of bond lengths. The linear relationships between magic and correlation are robust across the Hamiltonians in our dataset, but break down at bond lengths beyond the Coulson-Fischer point, where Hartree-Fock fails to capture key physical features of the true ground state wavefunction. By establishing linear relationships for both correlation energy and Hartree-Fock reference weight with the 2-SRE, we conclude that for weakly- and moderately-correlated electronic structure Hamiltonians, the correlation is directly represented by 2-SRE, and thus by the magic.
Electron correlation plays an important role in determining the properties of physical systems, from atoms and molecules to condensed phases. Recent theoretical progress in the field has proven possible using both analytical methods and numerical many-body treatments, for realistic systems as well as for simplified models. Within the models, one may mention the jellium and the Hubbard. The jellium model, while providing a simple, rough approximation to conduction electrons in metals, also constitutes a key ingredient in the treatment of electrons in condensed phases within density-functional formalism. The Hubbard- and the related Heisenberg-model Hamiltonians, on the other hand, are designed to treat situations in which very strong correlations tend to bring about site localization of electrons. The character of the interactions in these lattice models allows for a local treatment of correlations. This is achieved by the use of projection techniques that were first proposed by Gutzwiller for the multicenter problem, being the natural extension of the Coulson-Fischer treatment of the H2 molecule. Much work in this area is analytic or semianalytic and requires approximations. However, a full many-body treatment of both realistic and simplified models is possible by resorting to numerical simulations, i.e., to the so-called quantum Monte Carlo method. This method, which can be implemented in a number of ways, has been applied to atoms, molecules, and solids. In spite of continuing progress, technical problems still remain. Thus one may mention the fermion sign problem and the increase in computational time with the nuclear charge in atomic and related situations. Still, this method provides, to date, one of the most accurate ways to calculate correlation energies, both in atomic and in multicenter problems.
Electron correlation plays an important role in determining the properties of physical systems, from atoms and molecules to condensed phases. Recent theoretical progress in the field has proven possible using both analytical methods and numerical many-body treatments, for realistic systems as well as for simplified models. Within the models, one may mention the jellium and the Hubbard. The jellium model, while providing a simple, rough approximation to conduction electrons in metals, also constitutes a key ingredient in the treatment of electrons in condensed phases within density-functional formalism. The Hubbard- and the related Heisenberg-model Hamiltonians, on the other hand, are designed to treat situations in which very strong correlations tend to bring about site localization of electrons. The character of the interactions in these lattice models allows for a local treatment of correlations. This is achieved by the use of projection techniques that were first proposed by Gutzwiller for the multicenter problem, being the natural extension of the Coulson-Fischer treatment of the H2 molecule. Much work in this area is analytic or semianalytic and requires approximations. However, a full many-body treatment of both realistic and simplified models is possible by resorting to numerical simulations, i.e., to the so-called quantum Monte Carlo method. This method, which can be implemented in a number of ways, has been applied to atoms, molecules, and solids. In spite of continuing progress, technical problems still remain. Thus one may mention the fermion sign problem and the increase in computational time with the nuclear charge in atomic and related situations. Still, this method provides, to date, one of the most accurate ways to calculate correlation energies, both in atomic and in multicenter problems.