Finite-temperature full configuration interaction

Zhuangfei Kou, So Hirata

Research output: Contribution to journalArticle

Abstract

The exact basis-set values of various thermodynamic potentials of a molecule are evaluated by the finite-temperature full configuration-interaction (FCI) method using ab initio molecular integrals over Gaussiantype orbitals. The thermodynamic potentials considered are the grand partition function, grand potential, internal energy, entropy, and chemical potential in the grand canonical ensemble as well as the partition function, Helmholtz energy, internal energy, and entropy in canonical ensemble. Approximations to FCI that are accurate at low and high temperatures are proposed, implemented, and tested. The results of finite-temperature FCI and its approximations are compared with one another as well as with the results of finite-temperature zeroth-order manybody perturbation theory, in which the Fermi-Dirac statistics is exact. Analytical asymptotic properties in the lowor high-temperature limits of some of these thermodynamic potentials are also given.

Original languageEnglish (US)
Article number1487
Pages (from-to)1-9
Number of pages9
JournalTheoretical Chemistry Accounts
Volume133
Issue number6
DOIs
StatePublished - 2014

Keywords

  • Canonical ensemble
  • Configuration interaction
  • Fermi-Dirac statistics
  • Grand canonical ensemble
  • Partition function
  • Temperature
  • Thermodynamics

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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