Abstract Chapter 11 employs variational differential techniques and the Schwinger Action Principle to derive coupled-field Green’s function equations for a multi-component system, modeled as an interacting electron-hole-phonon system. The coupled Fermion Green’s function equations involve five interactions (electron-electron, hole-hole, electron-hole, electron-phonon, and hole-phonon). Starting with quantum Hamilton equations of motion for the various electron/hole creation/annihilation operators and their nonequilibrium average/expectation values, variational differentiation with respect to particle sources leads to a chain of coupled Green’s function equations involving differing species of Green’s functions. For example, the 1-electron Green’s function equation is coupled to the 2-electron Green’s function (as earlier), also to the 1-electron/1-hole Green’s function, and to the Green’s function for 1-electron propagation influenced by a nontrivial phonon field. Similar remarks apply to the 1-hole Green’s function equation, and all others. Higher order Green’s function equations are derived by further variational differentiation with respect to sources, yielding additional couplings. Chapter 11 also introduces the 1-phonon Green’s function, emphasizing the role of electron coupling in phonon propagation, leading to dynamic, nonlocal electron screening of the phonon spectrum and hybridization of the ion and electron plasmons, a Bohm-Staver phonon mode, and the Kohn anomaly. Furthermore, the single-electron Green’s function with only phonon coupling can be rewritten, as usual, coupled to the 2-electron Green’s function with an effective time-dependent electron-electron interaction potential mediated by the 1-phonon Green’s function, leading to the polaron as an electron propagating jointly with its induced lattice polarization. An alternative formulation of the coupled Green’s function equations for the electron-hole-phonon model is applied in the development of a generalized shielded potential approximation, analysing its inverse dielectric screening response function and associated hybridized collective modes. A brief discussion of the (theoretical) origin of the exciton-plasmon interaction follows.
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.
Identical Particles Second Quantization Independent-Particle Model for Fermions in Finite Systems Two-Particle States and Interactions Noninteracting Bosons and Fermions Propagators in One-Particle Quantum Mechanics Single-Particle Propagator in Many-Particle Systems Perturbation Expansion of the Single-Particle Propagator Dyson Equation and Self-consistent Green's Functions Mean-Field or Hartree-Fock Approximation Beyond the Mean-Field Approximation Interacting Boson Systems Excited States in Finite Systems Excited States in Infinite Systems Excited States in N 2 Systems and In-Medium Scattering Dynamical Treatment of the Self-energy in Infinite Systems Dynamical Treatment of the Self-energy in Finite Systems Bogoliubov Perturbation Expansion for the Bose Gas Boson Perturbation Theory Applied to Physical Systems In-Medium Interaction and Scattering of Dressed Particles Conserving Approximations and Excited States Pairing Phenomena Propagator Framework for Phenomenological Description of Many-Body Systems Finite Temperature Formalism and Applications.
Ab initio electron propagator methods are developed to study electronic properties of molecular systems with strong electron-electron and electron-phonon interactions. For the calculation of electron Green's functions we apply a canonical small polaron transformation that intrinsically contains strong electron-phonon effects. In the transformed Hamiltonian, the energy levels for the noninteracting particles are shifted down by the relaxation (solvation) energies. The Coulomb integrals are also renormalized by the electron-phonon interaction. For certain values of the electron-phonon coupling constants, the renormalized Coulomb integrals can be negative which implies the attraction between two electrons. Within the small polaron transformation we develop a diagrammatic technique for the calculation of electron Green's function in which the electron-phonon interaction is already included into the multiple phonon correlation functions. Since the decoupling of the phonon correlation functions is impossible, and therefore, a Wick's theorem for such correlation functions is invalid, there is no Dyson equation for the electron Green's function. To find the electron Green's function, we use different approximations. One of them is a link-cluster approximation that includes diagonal transitions for the renormalized zeroth Green's function. In the linked-cluster approach the Dyson equation is derived in the most general case, where the self-energy operator is an arbitrary functional (not only in the Hartree-Fock approximation). It is shown that even a Hartree-Fock electron (hole) is not a particle any longer. It is a quasiparticle with a finite lifetime that depends on energy of particle and hole states in different ways. As a consequence of this, a standard description of a Hartree-Fock approximation in terms of wave functions becomes inappropriate in this problem. To challenge the linked-cluster approximation we develop a different approach: a sequential propagation approximation where scattering events occur only for sequential transitions. A self-consistent Hartree-Fock equation for a four-index Green's function matrix is derived. In conclusion, the proposed schemes can be considered for future method developments for quantum chemical calculations for large molecules with strong nonadiabatic effects, e-e correlated electron transfer reactions, and electron transport in molecular transport junctions.
This is the first of a series of papers dealing with many-particle systems from a unified, nonperturbative point of view. It contains derivations and discussions of various field-theoretical techniques which will be applied in subsequent papers. In a short introduction the general method of approach is summarized, and its relationship to other field-theoretic problems indicated. In the second section the macroscopic properties of the spectra of many-particle systems are described. Asymptotic evaluations are performed which characterize these macroscopic features in terms of intensive parameters, and the relationship of these parameters to thermodynamics is discussed. The special characteristics of the ground state are shown to follow as a limiting case of the asymptotic evaluations. The third section is devoted to the time-dependent field correlation functions, or Green's functions, which describe the microscopic behavior of a multiparticle system. These functions are defined, and related to intensive macroscopic variables when the energy and number of particles are large. Spectral representations and other properties of various one-particle Green's functions are derived. In the fourth section the treatment of non-equilibrium processes is considered. As a particular example, the electromagnetic properties of a system are expressed in terms of the special two-particle Green's function which describes current correlation. The discussion yields specifically a fluctuation-dissipation theorem, a sum rule for conductivity, and certain dispersion relations. The fifth section deals with the differential equations which determine the Green's functions. The boundary conditions that characterize the Green's function equations are exhibited without reference to adiabatic decoupling. A method for solving the equations approximately, by treating the correlations among successively larger numbers of particles, is considered. The first approximation in this sequence is shown to yield a generalized Hartree-like equation. A related, but rigorous, identity for the single-particle Green's function is then derived. A second approximation, which takes certain two-particle correlations into account, is shown to produce various additional effects: The interaction between particles is altered in a manner characterized by the intensive macroscopic parameters, and the modification and spread of the energy-momentum relation come into play. In the final section compact formal expressions for the Green's functions and other physical quantities are derived. Alternative equations and systematic approximations for the Green's functions are obtained.
In describing transport phenomena, it is vital to build the conservation laws of number, energy, momentum, and angular momentum into the structure of the approximation used to determine the thermodynamic many-particle Green's functions. A method for generating conserving approximations has been developed. This method is based on a consideration, at finite temperature, of the equations of motion obeyed by the one-particle propagator
G, defined in the presence of a nonlocal external scalar field
U. Approximations for
G(U) are obtained by replacing the
G2(U) which appears in these equations by various functionals of
G(U). If the approximation for
G2(U) satisfies certain simple symmetry conditions, then the
G(U) thus defined obeys all the conservation laws. Furthermore, the two-particle correlation function, generated as ${(\frac{\ensuremath{\delta}G}{\ensuremath{\delta}U})}_{U=0}\ensuremath{\equiv}\ifmmode\pm\else\textpm\fi{}L$, in terms of which all linear transport can be described, will obey all the conservation laws as well as several essential sum rules, such as the longitudinal
f-sum rule.Several examples of conserving approximations are described. The Hartree approximation,
G2(U)=G(U)G(U), generates the random-phase approximation for
L. The Hartree-Fock approximation for
G(U) leads to a natural generalization of the random-phase approximation in which hole-particle ladder diagrams are summed. Another conserving approximation for
G(U) is obtained by expanding the self-energy to first order in the many-particle scattering matrix
T(U). This
T is obtained by summing ladder diagrams in which the sides of the ladder are composed of
G(U)′s. The resulting
L equation, which involves coefficients proportional to
∣T∣2, is analogous to the linearized version of the usual Boltzmann equation. Finally, in order to obtain a description of collisions in a plasma, the self-energy is expanded to first order in a dynamically shielded potential,
Vs(U). This potential is obtained by summing bubbles composed of two
G(U)′s. The resulting
L equation is similar in structure to a Boltzmann equation in which the collision cross section is proportional to
∣Vs∣2.