This chapter presents field-theoretic methods and discusses three well-known "pictures" or representations used in discussing quantum mechanical problems. It explores how to build up the true one-electron and one-phonon Green's functions as a perturbation series involving the corresponding functions for the non-interacting system. In elementary discussions of quantum mechanics one usually works in the "Schrodinger picture" in which the dynamical variables are taken to be time independent so that the wave function contains the time dependence of the problem. The one-electron Green's function gives information about the spin and charge densities and the momentum distribution of the electrons as well as information about the excitation spectrum of the system. When the system consists only of fermions interacting via an instantaneous two-body potential, the one-particle Green's function also suffices to determine the ground-state energy of the system. The electrical conductivity, magnetic susceptibility, and many other non-equilibrium properties can be obtained from the two-particle Green's function.
This chapter presents field-theoretic methods and discusses three well-known "pictures" or representations used in discussing quantum mechanical problems. It explores how to build up the true one-electron and one-phonon Green's functions as a perturbation series involving the corresponding functions for the non-interacting system. In elementary discussions of quantum mechanics one usually works in the "Schrodinger picture" in which the dynamical variables are taken to be time independent so that the wave function contains the time dependence of the problem. The one-electron Green's function gives information about the spin and charge densities and the momentum distribution of the electrons as well as information about the excitation spectrum of the system. When the system consists only of fermions interacting via an instantaneous two-body potential, the one-particle Green's function also suffices to determine the ground-state energy of the system. The electrical conductivity, magnetic susceptibility, and many other non-equilibrium properties can be obtained from the two-particle Green's function.
Within the Landauer approach to conduction discussed in the previous chapter, electron interactions have been included only at the mean-field level. This is quite a strong approximation, especially in nanojunctions, where large current densities are common. I therefore want to go beyond this level of description. I can follow two different routes. (1) I can develop a functional theory of quantum correlations via time-dependent effective single-particle equations, as I will do in Chapter 7 where I will use dynamical density-functional theories within the micro-canonical approach to conduction. (2) I can try to solve the time-dependent Schrödinger equation 1.16 – or its mixed-state version, the Liouville-von Neumann equation 1.60 – directly. Written this way, this last proposition seems hopeless. In reality, we can employ a many-body technique, known as the non-equilibrium Green's function formalism (NEGF), also referred to as the Keldysh formalism (Keldysh, 1964; Kadanoff and Baym, 1962), which allows us, at least in principle, to do just that: solve the time-dependent Schrödinger equation for an interacting many-body system exactly, from which one can, in principle, calculate the time-dependent current. This is done by solving equations of motion for specific time-dependent single-particle Green's functions, from which the physical properties of interest, such as the charge and current densities, can be obtained. I have stressed the term “time-dependent” several times, because, as I will show in a moment, the NEGF is “exact” only when one solves the time-dependent Schrödinger equation for a closed quantum system, subject to deterministic perturbations: the system is closed but not necessarily isolated. These perturbations may drive the system far away from its initial state of thermodynamic equilibrium (Keldysh, 1964).
In the previous chapter we studied the kinematics of many-body systems, and the form of operators representing the physical properties of a system, all of which were embodied by the quantum field. In this chapter we shall study the quantum dynamics of many-body systems, which can also be embodied by the quantum fields. We shall employ the fact that the quantum dynamics of a system, instead of being described in terms of the dynamics of the states or the evolution operator, i.e. as previously done through the Schrödinger equation, can instead be carried by the quantum fields. The quantum dynamics is therefore expressed in terms of the correlation functions or Green's functions of the quantum fields evaluated with respect to some state of the system. In particular we shall consider the general case of quantum dynamics for arbitrary non-equilibrium states. After introducing various types of Green's functions and relating them to measurable quantities, we will discuss the simplifications reigning for the special case of equilibrium states. Quantum dynamics Quantum dynamics can be described in different ways since quantum mechanics is a linear theory and the dynamics described by a unitary transformation of states. This will come in handy in the next chapter when we study a quantum theory in terms of its perturbative expansion using the so-called interaction picture. Here we first discuss the Schrödinger and Heisenberg pictures. The Schrödinger picture Having the Hamiltonian on the multi-particle space at hand we can consider the dynamics described in the multi-particle space.
Preparation, I have often said, is rightly two-thirds of any venture. Amelia Earhart Summary Correlation functions provide a direct way to characterize and analyze many-body systems, both theoretically and experimentally. In this chapter we review the properties of one- and two-body correlation functions in quantum systems, with emphasis on several key quantities: static density correlations that determine the energy and thermodynamic potentials, dynamic correlation functions such as response functions that describe excitations of the system, and Green's functions that are basic tools in the theory of interacting many-body systems. Correlation functions are central quantities in the description of interacting many-body systems, both in the theoretical formulation and in the analysis of experiments. In contrast to single numbers like the total energy, correlation functions reveal far more information about the electrons, how they arrange themselves, and the spectra of their excitations. In contrast to the many-body wavefunctions that contain all the information on the system, correlation functions extract the information most directly relevant to experimentally measurable properties. Dynamic current–current correlation functions are sufficient to determine the electrical and optical properties: one-body Green's functions describe the spectra of excitations when one electron is added to or removed from the system, static and dynamic correlations are measured using scattering techniques, and so forth. In this chapter we present the basic definitions and properties of correlation functions and Green's functions that are the basis for much of the developments in the following chapters. In general, a correlation function quantifies the correlation between two or more quantities at different points in space r , time t , or spin σ . Very often the correlation function can be specified as a function of the Fourier-transformed variables, momentum (wavevector) k , and frequency ω . It is useful to distinguish between a dynamic correlation function which describes the correlation between events at different times and a static or equal-time correlation function, by which we mean that of a property measured or computed with “snapshots” of the system. Also, the different correlation functions can be classified by the number of particles and/or fields involved.
To avoid confusion, it is necessary to be quite explicit about what is assumed and what is to be proved. A. Klein, Phys. Rev. 121, 950 (1961) Summary The topic of this chapter is functionals that provide a concise formulation for thermodynamic quantities and Green's function methods in interacting many-body systems. Building upon the instructive examples of density functional theory and the Hartree– Fock approximation, functionals of the Green's function are developed to provide a framework for practical methods used extensively in many-body perturbation theory (Chs. 9–15), dynamical mean-field theory (Chs. 16–20), and their combination in Ch. 21. Functional concepts give a firm foundation for those methods, for example, they give the conditions for approximations to obey conservation laws. Additional background and specific aspects are in App. H. Many physical quantities can be expressed as functionals , i.e., they depend on an entire function.1 For example, in the quantum variational method to determine a wavefunction, the total energy of a system of many electrons is a functional of a many-body trial wavefunction ( r 1 , r 2 , …): it is the expectation value of the hamiltonian. At the variational minimum, assuming the trial wavefunction is completely flexible, one finds the many-body Schrödinger equation for the ground state. Many of the properties we are interested in are, formally, simple functionals of the ground- or excited-state wavefunctions. In the search for feasible ways to calculate properties such as excitation spectra, we are led to different types of functional. The idea is to deal only with a physical, measurable quantity Q of interest and a variational functional E [ Q ] of this quantity. The variational character of E allows one to derive equations that determine Q 0 , the value of Q for the system in a desired state, typically the ground state or equilibrium state at T ≠ 0. Other properties should be different functionals F m [ Q ] that can then be evaluated at Q = Q 0 . This strategy is outlined in Fig. 8.1. To appreciate the power of such approaches, one can consider the impact of density functional theory, which is formulated as a functional of the density n ( r ) of electrons; it is defined for a range of densities and the variational minimum for the energy functional E [ n ] leads to equations to determine the actual ground-state density n 0 ( r ) and total energy E 0 .
This dissertation concerns the quantum many-body problem, which is the problem of predicting the properties of systems of several quantum particles from the first principles of quantum mechanics. Included under this umbrella are various problems of fundamental importance in quantum chemistry, condensed matter physics, and materials science. Of particular interest is the electronic structure problem, the problem of determining the state of the electrons in a system with fixed atomic nuclei. Since direct numerical solution of the many-body Schrödinger equation is intractable even for systems of moderate size, a diverse array of approximate methods has been developed. The broad goals of this dissertation are to improve the mathematical understanding of certain widely-used approximations, as well as to propose new methods. Roughly speaking, we consider three (overlapping) categories of methods: Green's function methods, embedding methods, and variational methods.One can understand Green's function methods in terms of many-body perturbation theory, which computes series expansions of physical quantities about a non-interacting reference system. These expansions can be expressed graphically in terms of Feynman diagrams, which can in turn be reorganized, in some cases, into an expansion in terms of so-called bold diagrams. Green's function methods can be specified by choosing a subset of bold diagrams to approximate the sum. At the same time, such methods can be understood in terms of an object known as the Luttinger-Ward (LW) functional, which admits a representation in terms of the bold diagrams. Many aspects of these constructions are purely formal, and indeed the existence of the fermionic LW functional as a single-valued functional has recently been called into question. To contribute to the understanding of these issues, we provide rigorous proofs of the combinatorial construction and analytic interpretation of the bold diagrams in the simplified setting of a classical field theory. In this setting we also provide a rigorous non-perturbative construction of the LW functional via convex duality and prove several key properties, including continuity up to the boundary of its domain and asymptotics in the limit of large interaction.Quantum embedding methods, meanwhile, view a large system as being composed of smaller fragments that are treated with high accuracy and embedded in the larger system in a mutually consistent way. Inspired by a connection between the boundary analysis of the LW functional and embedding, we perform similar analysis for the 1-RDM theory for fermionic systems, which is also developed via convex duality, illustrating a relation to fermionic embedding methods such as the density matrix embedding theory (DMET).Another embedding method of note is the dynamical mean-field theory (DMFT), which is at the same time a Green's function method that can be understood in terms of the LW functional. DMFT relies on the solution of impurity problems, which specify the embedding of an interacting system into a non-interacting bath. Underlying DMFT is a result about the sparsity pattern of the self-energy matrix for impurity problems, which to our knowledge has not been proved in the literature. We provide a rigorous proof of this result in various classical and quantum settings. We go on to investigate the fermionic DMFT in depth, identifying the key mathematical structures that appear in the algorithmic loop for solving it and using these to prove the well-posedness of this loop, in a certain sense.Finally, we introduce a suite of new approaches to the quantum many-body problem that provide variational lower bounds to the ground-state energy. These methods, which combine the themes of convexity and embedding, are based on novel convex relaxations of the variational principles for the ground-state energies of many-body systems. To begin, we recover a second-quantized version of the formalism of strictly correlated electrons (SCE), which yields an exact expression for the exchange-correlation functional in Kohn-Sham density functional theory in the limit of infinite Coulomb repulsion in terms of the solution of a multi-marginal optimal transport problem. We introduce a semidefinite relaxation method for approximately solving this problem and obtaining a lower bound for the ground-state energy. The ideas underlying this relaxation are generalized considerably, outside the context of SCE, to yield much tighter lower bounds, which we validate numerically for both quantum spin systems and fermionic systems. We also describe how these relaxation methods can be interpreted as embedding methods via convex duality.
Introduction Mathematically, given a linear differential operator L x , one encounters the solution to the inhomogeneous differential equation Here ρ ( x ) is a given source function. For a given boundary condition, we assume a solution to exist. The solution can be reduced to a simpler problem. Let G ( x, y ) is the Green's function. This is a function of x with y a parameter. Take G ( x, y ) to satisfy the same boundary conditions as φ ( x ). Then since An example of L x is, of course, the Schrödinger operator We take ρ ( x ) = V ( x ) ψ ( x , t ), ψ ( x , t ) being the wave function and V ( x ) the potential operator. We are interested in Green's functions taken over from the techniques of quantum field theory (Schweber, 1961; Lifshitz and Petaevskii, 1981). We will concern ourselves particularly with one- and two-time Green's functions, since our principal interest is to show a connection to the calculations of linear response theory (Chapter 15) as well as to quantum kinetic equations. Then we wish to compare the methods with those described in Chapter 4. In this we will follow the work of L. P. Kadanoff and G. Baym (1962) and of L. V. Keldysh (1965) and also Zubarev (1974). We will not discuss equilibrium statistical mechanics utilizing Green's function techniques for many-body problems. The literature is exhaustive (see Abrikosov et al. , 1963; Fetter and Walecka, 1971). A good general introduction is the book by G. D. Mahan (2000). One- and two-time quantum Green's functions and their properties Let us introduce the creation operator ψ † ( r, t ) and annihilation operator ψ ( r, t ) of the second quantization formalism (see Schweber, 1961). They have the equal time commutation rules for Bose and Fermi particles: The Hamiltonian operator for the particles is and the number density of particles at r t is the operator Note that r = ( r 1 … r N ) for (1, 2, 3, …, N ) and V (| r − r ′|) is the pair potential depending, as in Chapter 4, on the scalar distance between the particles.