Plane-Wave-Based Stochastic-Deterministic Density Functional Theory for Extended Systems

TL;DR

This paper introduces plane-wave-based stochastic-deterministic density functional theories (CT, SDFT, MDFT) implemented in ABACUS, offering accurate and efficient alternatives to traditional KSDFT for large, high-temperature extended systems.

Contribution

The paper develops and systematically evaluates plane-wave-based CT, SDFT, and MDFT methods within ABACUS, demonstrating their high accuracy and efficiency over traditional KSDFT for extended systems.

Findings

Methods reproduce KSDFT results with high accuracy

CT, SDFT, MDFT show advantages in efficiency and scalability

Suitable for high-temperature, large-scale systems like warm dense matter

Abstract

Traditional finite-temperature Kohn-Sham density functional theory (KSDFT) has an unfavorable scaling with respect to the electron number or at high temperatures. The evaluation of the ground-state density in KSDFT can be replaced by the Chebyshev trace (CT) method. In addition, the use of stochastic orbitals within the CT method leads to the stochastic density functional theory [Phys. Rev. Lett. 111, 106402 (2013)] (SDFT) and its improved theory, mixed stochastic-deterministic density functional theory [Phys. Rev. Lett. 125, 055002 (2020)] (MDFT). We have implemented the above four methods within the first-principles package ABACUS. All of the four methods are based on the plane-wave basis set with the use of norm-conserving pseudopotentials and the periodic boundary conditions with the use of $k$-point sampling in the Brillouin zone. By using the KSDFT calculation results as benchmarks, we systematically evaluate the accuracy and efficiency of the CT, SDFT, and MDFT methods via examining a series of physical properties, which include the electron density, the free energy, the atomic forces, stress, and density of states for a few condensed phase systems. The results suggest that our implementations of CT, SDFT, and MDFT not only reproduce the KSDFT results with a high accuracy, but also exhibit several advantages over the tradition KSDFT method. We expect these methods can be of great help in studying high-temperature and large-size extended systems such as warm dense matter and dense plasma.