Finite-temperature many-body perturbation theory in the grand canonical ensemble
Abstract
A finite-temperature many-body perturbation theory is presented that 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 zeroth-order thermal averages of one- through four-indexed quantities and of 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 temperature.
Keywords
Cite
@article{arxiv.2003.05540,
title = {Finite-temperature many-body perturbation theory in the grand canonical ensemble},
author = {So Hirata and Punit K. Jha},
journal= {arXiv preprint arXiv:2003.05540},
year = {2020}
}