Thermal quasi-particle theory

Fuente: arXiv
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Main Author: Hirata, So
Format: Preprint
Published: 2024
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author Hirata, So
author_facet Hirata, So
contents 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 (quasi-particle) 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 constitutes 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 may outperform the latter at intermediate temperature 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.
format Preprint
id arxiv_https___arxiv_org_abs_2408_03970
institution arXiv
publishDate 2024
record_format arxiv
spellingShingle Thermal quasi-particle theory
Hirata, So
Statistical Mechanics
Chemical Physics
Computational Physics
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 (quasi-particle) 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 constitutes 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 may outperform the latter at intermediate temperature 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.
title Thermal quasi-particle theory
topic Statistical Mechanics
Chemical Physics
Computational Physics
url https://arxiv.org/abs/2408.03970