One- and two-particle reduced density matrices have been calculated for a ``resonating'' Heitler-London wavefunction, in a system which is a finite model of a two-dimensional square planar lattice structure (4×4 net of one-electron atoms with Born-von Karman boundary conditions). The Heitler-London wavefunction describes the electronic ground state of a system with a single narrow half-filled band (the Mott insulator). Various measures of electron correlation (pair correlation functions, etc.) are defined and calculated. The intent of these calculations is to provide ``empirical'' guidelines for many-body methods for calculation of Green's functions for one and two particles (reduced density matrices are initial values for the respective Green's functions). Results show that the Heitler-London description is incompatible with several assumptions and widely used models for the Mott insulator. In particular it is found that (a) pair correlations in the Heitler-London ground state remain local even when ``resonance'' of an extremely large number of valence-bond structures occurs; the long range antiferromagnetic ordering obtained in several models of the Mott insulator (the ``two-sublattice'' or ``different bands for different spins'' models) does not occur. (b) The density matrix for the Heitler-London state does not exhibit a BCS type ``pair condensation'', as has been conjectured to describe the Mott insulator in some recent work. Our results strongly suggest that if the Heitler-London description is appropriate, the ``Hubbard Hamiltonian'', which includes only intraatomic pair interactions, does not offer an adequate model of the Mott insulator.
One- and two-particle reduced density matrices have been calculated for a resonating'' Heitler-London wavefunction, in a system which is a finite model of a two-dimensional square planar lattice structure (4×4 net of one-electron atoms with Born-von Karman boundary conditions). The Heitler-London wavefunction describes the electronic ground state of a system with a single narrow half-filled band (the Mott insulator). Various measures of electron correlation (pair correlation functions, etc.) are defined and calculated. The intent of these calculations is to provide empirical'' guidelines for many-body methods for calculation of Green's functions for one and two particles (reduced density matrices are initial values for the respective Green's functions). Results show that the Heitler-London description is incompatible with several assumptions and widely used models for the Mott insulator. In particular it is found that (a) pair correlations in the Heitler-London ground state remain local even when resonance'' of an extremely large number of valence-bond structures occurs; the long range antiferromagnetic ordering obtained in several models of the Mott insulator (the two-sublattice'' or different bands for different spins'' models) does not occur. (b) The density matrix for the Heitler-London state does not exhibit a BCS type pair condensation'', as has been conjectured to describe the Mott insulator in some recent work. Our results strongly suggest that if the Heitler-London description is appropriate, the ``Hubbard Hamiltonian'', which includes only intraatomic pair interactions, does not offer an adequate model of the Mott insulator.
A systematic procedure is described for calculating the reduced density matrices of first and second order for a resonating valence bond wavefunction on square planar nets with Born-von Karman boundary conditions of finite period. The density matrices explicitly display the electron correlation in such a wavefunction, which is a model ground state for a two-dimensional Mott insulator. Because of the extremely large number of contributing valence bond structures, it is essential to utilize their symmetry under the space group for minimum computation. For the totally symmetric singlet state described, density matrix eigenvectors form basis vectors for irreducible representations. The irreducible representations spanned by pair states on the square plane lattice are listed, and a set of irreducible basis vectors for the two-particle density matrix is defined which clearly displays the nature of electron pair correlations in such a system (correlated geminals). The apparatus has been employed in a calculation described in the paper accompanying this one (succeeding article).
We investigate the ground state (T = 0 K) of the one-dimensional symmetrical (n = 1) Hubbard model formalized in terms of the system of integral equations, which we previously obtained using the method of the generating functional of Green’s functions with the subsequent Legendre transformation. In a wide range of variations in the parameter of Coulomb interaction U, the following characteristics of the system have been calculated: the electron density of states, the electron band spectrum, the number of doubly occupied lattice sites, the localized magnetic moment, the correlator of the square of the longitudinal component of spin at a site,<S Z 2>, and the internal energy of the system. It has been shown that, for all U > 0, the model yields two solutions, i.e., an antiferromagnetic insulator and a paramagnetic insulator, in which there are no single-electron quasi-particles at the Fermi level. The energy of the paramagnetic solution in the region of U < 1.1 is considerably less than that of the antiferromagnetic solution for the case of U > 1.1, we have the opposite situation.
In this thesis we consider a variational wave function approach as a possible route to describe the competition between disorder and strong electron-electron interaction in two dimensions. In particular we aim to obtain a transparent and physically intuitive understanding of the competition between these two localizing forces within the simplest model where they both are active, namely the disordered Hubbard model at half filling and in a square lattice. Our approach is based on an approximate form of the ground-state wave function, which we believe contains the physically relevant ingredients for a correct description of both the Mott and the Anderson insulators, where electrons are localized by the Coulomb repulsion and by disorder, respectively. For strongly interacting fermionic systems, a standard variational wave function is constructed by a correlation term acting on a Slater determinant, the latter being an uncorrelated metallic state. Previous variational calculations showed that a long-range density-density correlation factor, so called Jastrow factor, is needed to correctly describe the Mott insulator [9]. This term, which is collective by definition, correlates spatially charge uctuations, thus preventing their free motion that would otherwise imply metallic conductance. For this reason, our variational wave function does include such a term. Anderson localization is instead mostly a matter of single-particle wave functions, hence it pertains to the uncorrelated Slater determinant which the Jastrow factor acts onto. We consider both the case in which we enforce paramagnetism in the wave function and the case in which we allow for magnetic ordering. Summarizing briefly our results, we find that, when the variational wave function is forced to be paramagnetic, the Anderson insulator to Mott insulator transition is continuous. This transition can be captured by studying several quantities. In particular, a novel one that we have identified and that is easily accessible variationally is the disconnected density-density fluctuation at long wavelength, defined by lim where ^nq is the Fourier transform of the charge density at momentum q, (...) denotes quantum average at fixed disorder and the overbar represents the average over disorder configurations. We find that Ndisc q!0 is everywhere finite in the Anderson insulator and vanishes critically at the Mott transition, staying zero in the Mott insulator. When magnetism is allowed and the hopping only connects nearest neighbor sites, upon increasing interaction the paramagnetic Anderson insulator first turns antiferromagnetic and finally the magnetic and compressible Anderson insulator gives way to an incompressible antiferromagnetic Mott insulator. The optimized uncorrelated Slater determinant is always found to be the eigenstate of a disordered non-interacting effective Hamiltonian, which suggests that the model is never metallic. Finally, when magnetism is frustrated by a next to nearest neighbor hopping, the overall sequence of phases does not change. However, the paramagnetic to magnetic transition within the Anderson insulator basin of stability turns first order. Indeed, within the magnetically ordered phase, we find many almost degenerate paramagnetic states with well defined local moments. This is suggestive of an emerging glassy behavior when the competition between disorder and strong correlation is maximum.
A Tribute to A. John Coleman - The Tame Mathematician.- Reduced Density Matrices: 1929-1989.- Some Aspects on the Development of the Theory of Reduced Density Matrices and the Representability Problem.- Representability Conditions.- On the Diagonal N-Representability Problem.- Fermion N-Representability Conditions Generated by a Decomposition of the 1-Particle Identity Operator onto Mutually Orthogonal Projection Operators.- The Unitarily Invariant Decomposition of Hermitian Operators.- Building Up N-Electron States with Symplectic Symmetry.- Time Dependent Antisymmetrized Geminal Power Theory Using a Coherent State Formulation.- Griffiths Inequalities for Fermion Systems.- Entropy of Reduced Density Matrices.- A Lower Bound to the Ground State Energy of a Boson System With Fermion Source.- Reduced Density Operators, Their Related von Neumann Density Operators, Close Cousins of These, and Their Physical Interpretation.- Theory and Practice of the Spin-Adapted Reduced Hamiltonians (SRH).- Variational Principle with Built-In Pure State N-Representability Conditions. The N-Electron Case.- Wigner Distributions as Representations of the Density Matrix.- Inter-Relationships Between Various Representations of One-Matrices and Related Densities: A Road Map and an Example ..- Current Problems in Density Functional Theory.- The Interface Between Reduced Density Matrices and Density Functional Theory.- The Physics Underlying the Langreth-Mehl Scheme for Non-Uniform Systems.- Understanding Energy Differences in Density Functional Theory.- Density Functional Calculations of Molecular Bond Energies.- Non-Local Effects on Atomic and Molecular Correlation Energies Studied with a Gradient-Corrected Density Functional.- An Evaluation of Local Electron Correlation Corrections and Non-Local Exchange Corrections to the Hartree-Fock-Slater Method from Calculations on Bond Energies and Electronic Spectra of Molecular Systems.- Correlation Energy Functionals of One-Matrices and Hartree-Fock Densities.- Some Remarks on Scaling Relations in Density Functional Theory.- Deduction of Semiempirical MO Methods from Density Functional Theory.- Charge and Spin Densities in Molecular Solids: Local Density Functional Calculations Versus Experiment.- A Functional of the Two-Particle Density Matrix for the Approximate Calculation of the Electronic Correlation Energy.- Extracules, Intracules, Correlation Holes, Potentials, Coefficients and All That.- The Exact Schroedinger Equation for the Electron Density.- Adiabatic Separation, Broken Symmetries and Geometry Optimization.- Asymptotic Results for Density Matrices and Electron Density in Atoms and Nearly Spherical Molecules.- An Algorithm for Calculating Isoelectronic Changes in Energies, Densities, and One-Matrices.- Atoms and Ions in the Limit of Large Nuclear Charge.- Improved Thomas-Fermi Theory for Atoms.- A Bond Energy from Quantum Mechanics.- Measured Electron Densities and Band Structure Calculations.- X-ray Orthonormal Orbital Model for Crystallography.
In no wave function of the type (1) [product of single determinants for each spin] is there a statistical correlation between the positions of the electrons with antiparallel spin. The purpose of the aforementioned generalization of (1) is to allow for such correlations. This will lead to an improvement of the wave function and, therefore, to a lowering of the energy value. E. Wigner, Phys. Rev. 46, 1002 (1934) Summary Although the exact many-body wavefunction cannot be written down in general, we do know of some of its properties. For example, there are differences between the wavefunctions of insulators and metals and the cusp condition gives the behavior as any two charges approach each other. In this chapter we also discuss approximate wavefunctions, ways to judge their accuracy and how to include electronic correlation. Examples of many-body wavefunctions are the Slater–Jastrow (pair product) wavefunction and its generalization to pairing and backflow wavefunctions. In other places in this book, we argue that it is not necessary to look at the many-body wavefunctions explicitly because they are unwieldy; the one- and two-body correlation functions discussed in Ch. 5 are sufficient to determine the energy and give information on the excitation spectra. However, these correlation functions do not always contain all information of interest. In principle, the ground-state energy of a many-electron system is a functional of the density, but the very derivation of the theorem invokes the many-body wavefunction, as expressed explicitly in Eq. (4.16). The effects of antisymmetry are manifest in the correlation functions, but antisymmetry is most simply viewed as a property of the wavefunction; electronic correlation is fundamentally a result of properties of the many-body wavefunction. Studying many-body wavefunctions provides a very useful, different point of view of many-body physics from the approaches based on correlation functions. Many of the most important discoveries in physics have come about by understanding the nature of wavefunctions, such as the Laughlin wavefunction for the fractional quantum Hall effect, the BCS wavefunction for superconductors, p-wave pairing in superfluid 3 He, and the Heitler– London approach for molecular binding. The role of Berry's phases has brought out the importance of the phase of the wavefunction in determining properties of quantum systems. This has led to new understanding of the classification of insulators, metals, superconductors, vortices, and other states of condensed matter.