The widely used thermal Hartree-Fock (HF) theory is generalized to include the effect of electron correlation while maintaining its quasi-independent-particle framework. An electron-correlated internal energy (or grand potential) is postulated in consultation with the second-order finite-temperature many-body perturbation theory (MBPT), which then dictates the corresponding thermal orbital (quasiparticle) energies in such a way that all fundamental thermodynamic relations are obeyed. The associated density matrix is of a one-electron type, whose diagonal elements take the form of the Fermi-Dirac distribution functions, when the grand potential is minimized. The formulas for the entropy and chemical potential are unchanged from those of Fermi-Dirac or thermal HF theory. The theory thus stipulates a finite-temperature extension of the second-order Dyson self-energy of one-particle many-body Green's function theory and can be viewed as a second-order, diagonal, frequency-independent, thermal inverse Dyson equation. At low temperatures, the theory approaches finite-temperature MBPT of the same order, but it may outperform the latter at intermediate temperatures by including additional electron-correlation effects through orbital energies. A physical meaning of these thermal orbital energies is proposed (encompassing that of thermal HF orbital energies, which has been elusive) as a finite-temperature version of Janak's theorem.
The widely used thermal Hartree-Fock (HF) theory is generalized to include the effect of electron correlation while maintaining its quasi-independent-particle framework. An electron-correlated internal energy (or grand potential) is postulated in consultation with the second-order finite-temperature many-body perturbation theory (MBPT), which then dictates the corresponding thermal orbital (quasiparticle) energies in such a way that all fundamental thermodynamic relations are obeyed. The associated density matrix is of a one-electron type, whose diagonal elements take the form of the Fermi-Dirac distribution functions, when the grand potential is minimized. The formulas for the entropy and chemical potential are unchanged from those of Fermi-Dirac or thermal HF theory. The theory thus stipulates a finite-temperature extension of the second-order Dyson self-energy of one-particle many-body Green's function theory and can be viewed as a second-order, diagonal, frequency-independent, thermal inverse Dyson equation. At low temperatures, the theory approaches finite-temperature MBPT of the same order, but it may outperform the latter at intermediate temperatures by including additional electron-correlation effects through orbital energies. A physical meaning of these thermal orbital energies is proposed (encompassing that of thermal HF orbital energies, which has been elusive) as a finite-temperature version of Janak's theorem.
A comprehensive and detailed account is presented for the finite-temperature many-body perturbation theory for electrons that expands in power series all thermodynamic functions on an equal footing. Algebraic recursions in the style of the Rayleigh-Schrödinger perturbation theory are derived for the grand potential, chemical potential, internal energy, and entropy in the grand canonical ensemble and for the Helmholtz energy, internal energy, and entropy in the canonical ensemble, leading to their sum-over-states analytical formulas at any arbitrary order. For the grand canonical ensemble, these sum-over-states formulas are systematically transformed to sum-over-orbitals reduced analytical formulas by the quantum-field-theoretical techniques of normal-ordered second quantization and Feynman diagrams extended to finite temperature. It is found that the perturbation corrections to energies entering the recursions have to be treated as a nondiagonal matrix, whose off-diagonal elements are generally nonzero within a subspace spanned by degenerate Slater determinants. They give rise to a unique set of linked diagrams-renormalization diagrams-whose resolvent lines are displaced upward, which are distinct from the well-known anomalous diagrams of which one or more resolvent lines are erased. A linked-diagram theorem is introduced that proves the size-consistency of the finite-temperature many-body perturbation theory at any order. General-order algorithms implementing the recursions establish the convergence of the perturbation series toward the finite-temperature full-configuration-interaction limit unless the series diverges. The normal-ordered Hamiltonian at finite temperature sheds light on the relationship between the finite-temperature Hartree-Fock and first-order many-body perturbation theories.
A finite-temperature many-body perturbation theory is presented, which expands in power series the electronic grand potential, chemical potential, internal energy, and entropy on an equal footing. Sum-over-states and sum-over-orbitals analytical formulas for the second-order perturbation corrections to these thermodynamic properties are obtained in a time-independent, nondiagrammatic, algebraic derivation, relying on the sum rules of the Hirschfelder–Certain degenerate perturbation energies in a degenerate subspace as well as nine algebraic identities for the zeroth-order thermal averages of one- through four-indexed quantities and products thereof. They reproduce numerically exactly the benchmark data obtained as the numerical derivatives of the thermal-full-configuration-interaction results for a wide range of temperatures.
Second-order many-body perturbation theory [MBPT(2)] is the lowest-ranked member of a systematic series of approximations convergent at the exact solutions of the Schrödinger equations. It has served and continues to serve as the testing ground for new approximations, algorithms, and even theories. This article introduces this basic theory from a variety of viewpoints including the Rayleigh-Schrödinger perturbation theory, the many-body Green's function theory based on the Dyson equation, and the related Feynman-Goldstone diagrams. It also explains the important properties of MBPT(2) such as size consistency, its ability to describe dispersion interactions, and divergence in metals. On this basis, this article surveys three major advances made recently by the authors to this theory. They are a finite-temperature extension of MBPT(2) and the resolution of the Kohn-Luttinger conundrum, a stochastic evaluation of the correlation and self-energies of MBPT(2) using the Monte Carlo integration of their Laplace-transformed expressions, and an extension to anharmonic vibrational zero-point energies and transition frequencies based on the Dyson equation.
Several closely related ab initio thermal mean-field theories for fermions, both well-established and new ones, are compared with one another at the formalism level and numerically. The theories considered are Fermi-Dirac theory; thermal Hartree-Fock (HF) theory; two modifications of the thermal single-determinant approximation of Kaplan and Argyres, Ann. Phys. 92, 1-24 (1975); and the first-order finite-temperature many-body perturbation theory based on a zero-temperature or thermal HF reference. Thermal full-configuration-interaction theory is used as the benchmark.
The individual particle theory of many body systems was studied starting from a microscopic point of view. A technique which is equivalent to a generalized thermodynamics was used to show that, under the appropriate conditions of temperature and external field, the quasi-particle approach is correct for three very dissimilar systemsi the normal degenerate Fermi system, the metallic electron-phonon system, and the polaron. The fact that an approach like this works for such dissimilar systems emphasizes the underlying unity of the quasi-particle models. The concept that the real t~me non-equilibrium self-energy and the incoherent part of the density-density correlation function may be generated as functional derivatives of a generalized thermodynamic potential (~), together with local translational and rotational invariance and Galilean relativity, leads to a transformation from the microscopic particle density variables g«p,m,R,T) to those of the quasi-particle theory n (R,T). ~ - p- It was shown that, for zero temperature, such a ~ derivability is exact; at low temperature and for slowly varying fields, this ~ derivability is approximately true. This was shown by a procedure which is eqUivalent to an expansion in terms of the real scattering probability for quasiparticles. At low temperature and for slowly varying fields, such real scattering is very improbable and the expansion parameter is small. Perturbation theory was used only to determine the actual size of terms which, on physical grounds are necessarily small. As such, this approach is non-perturbative, depending only on properties of the exact selfenergies and correlation functions. In addition to demonstrating that the quasi-particle models are correct, information on the regions of validity for ~hese models is obtained. .As by-products of these derivations, microscopic expressions for the parameters of the quasi-particle theory and simple microscopic expressions for the currents in degenerate Fermi systems and the electron-phonon system are obtained.
In Chapter 6, we derived a generalized Gross–Pitaevskii condensate equation which is coupled to a kinetic equation for the distribution function for the thermal atoms. However, the kinetic equation in Chapter 6 is only valid in the semiclassical limit. It involves the assumption that the thermal energy k B T is much greater than the spacing between the harmonic trap energy levels ( k B T ≫ω 0 where ω 0 is the trap frequency) and also much greater than the average interaction energy ( k B T ≫ gn ). The ZNG model, based on HF excitations, is still expected to be adequate down to quite low temperatures in trapped Bose gases, as will be shown by the results in Chapter 12. However, the ZNG model will break down at very low temperatures, where the Hartree–Fock excitations must be replaced by the Bogoliubov spectrum. To deal with this, one has to derive a kinetic equation for the Bogoliubov quasiparticle excitations. This is the goal of the present chapter. In this chapter, we use the second-order Beliaev approximation to discuss the nonequilibrium dynamics of a trapped Bose-condensed gas at finite temperatures. In doing to, we combine the second-order Beliaev self-energies with the lower-order Bogoliubov excitation spectrum, including off-diagonal single-particle propagators but still omitting the anomalous correlation functions. This last condition defines the Bogoliubov–Popov approximation. In this chapter, we consider only the damping which arises from collisions. We will not explicitly calculate corrections that are second-order in g to the quasiparticle energy spectrum or to the condensate chemical potential, both of which are associated with the real parts of the second-order Beliaev self-energies. The present chapter is a natural generalization of work presented in Chapter 6 for the simpler HF excitation spectrum assumed in the ZNG analysis.