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arXiv · 2003.05540

Finite-temperature many-body perturbation theory in the grand canonical ensemble

So Hirata·Punit K. Jha
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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.

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So Hirata, Punit K. Jha. 2020-03-11. Finite-temperature many-body perturbation theory in the grand canonical ensemble. https://doi.org/10.1063/5.0009679

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