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

So Hirata, Punit K. Jha

Research output: Contribution to journalArticle

Abstract

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.

Original languageEnglish (US)
Article number014103
JournalJournal of Chemical Physics
Volume153
Issue number1
DOIs
StatePublished - Jul 7 2020

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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