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 language | English (US) |
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Article number | 014103 |
Journal | Journal of Chemical Physics |
Volume | 153 |
Issue number | 1 |
Early online date | Jul 1 2020 |
DOIs | |
State | Published - Jul 7 2020 |
ASJC Scopus subject areas
- General Physics and Astronomy
- Physical and Theoretical Chemistry