Thermal quasi-particle theory

Abstract

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 defined by the second-order finite-temperature many-body perturbation theory (MBPT), which then dictates the corresponding thermal orbital (quasi-particle) energies in such a way that all thermodynamic relations are obeyed. The associated density matrix is of the 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 postulates 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 temperature, the theory approaches finite-temperature MBPT of the same order, but it outperforms the latter at intermediate temperature by including additional electron-correlation effects through orbital energies. A physical meaning of these thermal orbital energies (including that of thermal HF orbital energies, which has been elusive) is proposed.