Numerical evidence invalidating finite-temperature many-body perturbation theory

Punit K. Jha, So Hirata

Research output: Chapter in Book/Report/Conference proceedingChapter

Abstract

Low-order perturbation corrections to the electronic grand potential, internal energy, chemical potential, and entropy of an ideal gas of noninteracting, identical molecules at a nonzero temperature are determined numerically as the λ-derivatives of the respective quantity calculated exactly (by thermal full configuration interaction) with a perturbation-scaled Hamiltonian, Hˆ0+λVˆ. The data thus obtained from the core definition of any perturbation theory serve as a benchmark against which analytical formulas can be validated. The first- and second-order corrections from finite-temperature many-body perturbation theory discussed in many textbooks disagree with these benchmark data. This is because the theory neglects the variation of chemical potential with λ, thereby failing to converge at the exact, full-interaction (λ = 1) limit, unless the exact chemical potential is known in advance. The renormalized finite-temperature perturbation theory (Hirata and He, 2013) (15) is also found to be incorrect.

Original languageEnglish (US)
Title of host publicationAnnual Reports in Computational Chemistry
EditorsDavid A. Dixon
PublisherElsevier Ltd
Pages3-15
Number of pages13
ISBN (Print)9780128171196
DOIs
StatePublished - 2019

Publication series

NameAnnual Reports in Computational Chemistry
Volume15
ISSN (Print)1574-1400
ISSN (Electronic)1875-5232

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Keywords

  • Chemical potential
  • Grand canonical ensemble
  • Grand potential
  • Internal energy
  • Many-body perturbation theory
  • Temperature
  • Thermodynamics

ASJC Scopus subject areas

  • Chemistry(all)
  • Computational Mathematics

Cite this

Jha, P. K., & Hirata, S. (2019). Numerical evidence invalidating finite-temperature many-body perturbation theory. In D. A. Dixon (Ed.), Annual Reports in Computational Chemistry (pp. 3-15). (Annual Reports in Computational Chemistry; Vol. 15). Elsevier Ltd. https://doi.org/10.1016/bs.arcc.2019.08.002