On the chemical potential of many-body perturbation theory in extended systems

TL;DR

This paper demonstrates that in extended systems, the chemical potential's influence on properties per electron diminishes in the infinite-size limit, allowing for more efficient correlation energy calculations at finite temperature.

Contribution

It establishes that the exchange-correlation free energy converges to the grand potential at a non-interacting chemical potential, reducing computational costs in many-body perturbation theory.

Findings

Infinite-size limit of exchange-correlation free energy matches grand potential at non-interacting chemical potential.

Regularization of Coulomb interaction reduces computational complexity by limiting interactions.

Numerical results for warm uniform electron gas validate the theoretical approach.

Abstract

Many methods for computing electronic correlation effects at finite temperature are related to many-body perturbation theory in the grand-canonical ensemble. In most applications, however, the average number of electrons is known rather than the chemical potential, requiring that expensive correlation calculations must be repeated iteratively in search for the chemical potential that yields the desired average number of electrons. In extended systems with mobile charges, however, the long-ranged electrostatic interaction should guarantee that the average ratio of negative and positive charges is one for any finite chemical potential. All properties per electron are virtually independent of the chemical potential, as for instance in an electric wire at different voltage potentials. This work shows that the infinite-size limit of the exchange-correlation free energy agrees with the infinite-size limit of the exchange-correlation grand potential at a non-interacting chemical potential. The latter requires only one expensive correlation calculation for each system size. Analogous to classical simulations of long-range-interacting particles, this work uses a regularization of the Coulomb interaction such that each electron on average interacts only with as many electrons as there are electrons in the simulation, avoiding interactions with periodic images. Numerical calculations of the warm uniform electron gas have been conducted with the Spencer--Alavi regularization employing the finite-temperature Hartree approximation for the self-consistent field and linearized finite-temperature direct-ring coupled cluster doubles for treating correlation.