A comprehensive account of the quantum theory of many particle systems is reported in this chapter. Essential features of a system of N-indistinguishable Bosonic and Fermionic particles, the exchange operator, space and spin dependent parts of wave function, properties of ground and excited states of the helium atom with detailed derivations for direct and exchange integrals, Hartree and Hartree-Fock approximations, and Thomas-Fermi and density functional theories for systems of N-particles are the contents of the chapter. Carefully chosen solved examples and unsolved exercises, which demonstrate how to deal with a system of more than a particle are included towards the end of chapter. The elaborated discussions on Hartree and Hartree-Fock approximations and Thomas-Fermi and density functional theories for systems of N-particles are special feature of this chapter.
A comprehensive account of the quantum theory of many particle systems is reported in this chapter. Essential features of a system of N-indistinguishable Bosonic and Fermionic particles, the exchange operator, space and spin dependent parts of wave function, properties of ground and excited states of the helium atom with detailed derivations for direct and exchange integrals, Hartree and Hartree-Fock approximations, and Thomas-Fermi and density functional theories for systems of N-particles are the contents of the chapter. Carefully chosen solved examples and unsolved exercises, which demonstrate how to deal with a system of more than a particle are included towards the end of chapter. The elaborated discussions on Hartree and Hartree-Fock approximations and Thomas-Fermi and density functional theories for systems of N-particles are special feature of this chapter.
Part 1 Fundamentals and examples: systems of identical particles second quantization for fermions second quantization for bosons unitary transformations and field operators example - the Hamiltonian of translationally invariant systems in second quantization density operators the Hartree-Fock approximation restricted Hartree-Fock approximation and the symmetry dilemma Hartree-Fock for translationally invariant systems the homogeneous electron gas in the Hartree-Fock approximation long-range correlations in the electron-gas - plasmons phonons superconductivity. Part 2 Green's functions: pictures the single-particle Green's function and the hierarchy of equations of motion. Part 3 Perturbation theory: time-dependent perturbation theory with adiabatic turning-on of the interaction particle and hole operators and Wick's theorem Feynman diagrams diagrammatic calculation of the vacuum amplitude an example - the Gell-Mann-Brueckner correlation energy of a dense electron gas diagrammatic calculation of the single-particle Green's function - Dyson's equation diagrammatic analysis of the Green's function G(kappa, omega) self-consistent perturbation theory, higher-order Hartree-Fock theory the quasi-particle concept diagrammatic calculation of the two-particle Green's function and the polarization propagator effective interaction and dressed vertices plasmons in higher order perturbation theory at finite temperatures. Part 4 Fermi liquid theory: introduction equilibrium properties transport equation and collective modes microscopic derivation of the Landau fermi liquid theory applications to the Kondo problem.
A system of N antisymmetric particles, moving under the influence of a fixed potential and their mutual many-particle interactions, is investigated in the ordinary Hartree-Fock scheme, having the total wave function approximated by a single Slater determinant. It is shown that all the density matrices of various orders, the wave function, and the entire physical situation depends only on a fundamental invariant $\ensuremath{\rho}({x}_{1}, {x}_{2})$, which is identical with the first-order density matrix. The Hartree-Fock equations are expressed in terms of this quantity.The Hartree-Fock equations are also solved by expanding the eigenfunctions in a given complete set, and applications to the MO-LCAO theory of the electronic structure of molecules, and crystals are given. It is shown that, in this scheme, the entire physical situation depends on a charge- and bond-order matrix $R(\ensuremath{\nu}\ensuremath{\mu})$ with respect to the ordinary atomic spin-orbitals involved. The Hartree-Fock equations for this matrix are investigated.Finally, the ionized and excited states are investigated, and it is shown that the Hartree-Fock scheme has a high degree of physical visuality also in case of many-particle interactions. The excitation energy of the system is the difference (${{\ensuremath{\omega}}_{j}}^{\ensuremath{'}}\ensuremath{-}{\ensuremath{\omega}}_{i}$) between two "spin-orbital energies," being eigenvalues to the effective Hamiltonians associated with the two states under consideration.
By means of a quantum mechanical phase space distribution function
introduced by von Roos, the Schroedinger equation for a non-relativistic
system of N identical particles with scalar interactions is transformed
into a quantum mechanical generalization of the Liouville equation,
thereby formulating the problem in terms of a generalized density in
phase space, a quantity of primary interest in most treatments of the
corresponding classical system (or plasma). This transformation permits
a parallel development of the theories of classical and quantum plasmas
and thus allows the quantum many-body problem to be discussed virtually
completely in classical terms. In particular, a kinetic theory of
quantum plasmas is obtained by deriving the quantum analogue of the BBGKY
hierarchy, and applying thereto approximation techniques similar to those
of Rostocker and Rosenbluth, and Bogoliubov. The point of departure from
similar previous studies based on the Wigner distribution function is that
the proper exchange symmetry can be tractably introduced into the formalism. Attention is first focused on the Hartree and Hartree-Fock approximations,
in which case the quantum BBGKY system reduces to a simple quantum
generalization of the Vlasov equation. This equation is used to study
the response of spatially homogeneous systems to weak external forces,
and the associated problems of plasmon and spin-wave excitations. It is
also used to derive the quantum and exchange corrected equations of
inviscid hydrodynamical transport which are then applied to the problem
of sound propagation in the degenerate electron gas. The second part of the study is concerned with the theory of the
many-electron atom in the Hartree and Hartree-Fock approximations.
The relevant quantum Vlasov equations lead naturally to a statistical
theory of the atom which reduces to the Thomas-Fermi-Amaldi and Thomas Fermi
models (respectively) as ħ → 0. For ħ ≠ 0, the quantum and
exchange corrections to these models are simultaneously generated. The
quantum hydrodynamical theory developed earlier is used to determine
the influence of these corrections on the boundary conditions of the
model, and a theory of the compressed atom is consequently obtained.
Considered in somewhat less detail are the effects of non-zero temperature,
net orbital angular momentum, relativity and correlations, as well as
time dependent processes. The final part deals with the problem of the degenerate electron
gas with a uniform neutralizing background. Going beyond the Hartree-Fock approximation, the pair functions for particles with
parallel and anti-parallel spin are obtained by neglecting three particle
correlations. From these functions, a quantum-mechanical collision
integral is derived which differs from that obtained by Silin
and Guernsey and conjectured by Wyld and Pines in that dynamical exchange
effects are included. Also obtained from the pair function
is an expression for the correlation which reduces in the high
density limit to the result of Gell-Mann and Brueckner. At intermediate
densities an additional term appears in the energy due to the screening
of the exchange interaction by the dielectric properties of the medium.
It is evaluated in the high density limit and found to be -0.151 r_s ln r_s
Ryd/electron in marked disagreement with the corresponding value obtained
by DuBois.
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 .
Chapter 15 is devoted to systems of identical particles and the associated quantum statistics. It is shown how the spin (whether integer or half-integer) determines fundamental features of the system’s behavior that cannot be obtained by approximate methods, in particular the exchange effects characteristic of states of two or more identical particles. The spin-symmetry relation is discussed in detail for both the Bose–Einstein and the Fermi–Dirac statistics. Quantum collective phenomena that are a defining feature of condensed matter, including phonons, superconductivity, Bose–Einstein condensates and the quantum Hall effect, are briefly introduced. Since most real quantum systems consist of subsystems in different quantum states that are mixtures of pure states, the chapter includes an introduction to the density matrix, its basic properties and its application to quantum statistics. It concludes with a critical discussion of decoherence and the significance of the collapse of the wave function.
The ground-state wave function and energy of a finite system of interacting fermions are expanded in terms of multiple-particle excitations on an uncorrelated zero-order state. The resulting set of coupled equations constitutes a systematic variational generalization of Hartree-Fock theory. Comparison is made with many-body perturbation theory and it is shown that to any order the theory incorporates an infinite number of perturbation theory terms. Solutions of the equations for ground-state atomic systems are discussed and related to previous work using many-body perturbation theory. It is shown that the sums of perturbation terms necessary for convergence are automatically included in the equations for two-particle excitations. Application of the equations to open-shell atoms is described.