Orbital-Free Density Functional Theory: An Attractive Electronic Structure Method for Large-Scale First-Principles Simulations

Kohn-Sham Density Functional Theory (KSDFT) is the most widely used electronic structure method in chemistry, physics, and materials science, with thousands of calculations cited annually. This ubiquity is rooted in the favorable accuracy vs cost balance of KSDFT. Nonetheless, the ambitions and expectations of researchers for use of KSDFT in predictive simulations of large, complicated molecular systems are confronted with an intrinsic computational cost-scaling challenge. Particularly evident in the context of first-principles molecular dynamics, the challenge is the high cost-scaling associated with the computation of the Kohn-Sham orbitals. Orbital-free DFT (OFDFT), as the name suggests, circumvents entirely the explicit use of those orbitals. Without them, the structural and algorithmic complexity of KSDFT simplifies dramatically and near-linear scaling with system size irrespective of system state is achievable. Thus, much larger system sizes and longer simulation time scales (compared to conventional KSDFT) become accessible; hence, new chemical phenomena and new materials can be explored. In this review, we introduce the historical contexts of OFDFT, its theoretical basis, and the challenge of realizing its promise via approximate kinetic energy density functionals (KEDFs). We review recent progress on that challenge for an array of KEDFs, such as one-point, two-point, and machine-learnt, as well as some less explored forms. We emphasize use of exact constraints and the inevitability of design choices. Then, we survey the associated numerical techniques and implemented algorithms specific to OFDFT. We conclude with an illustrative sample of applications to showcase the power of OFDFT in materials science, chemistry, and physics.

Automated summary

Kohn-Sham Density Functional Theory (KSDFT) is widely used in chemistry, physics, and materials science, but its computational cost limits its application in large molecular systems. Orbital-free DFT (OFDFT) overcomes this limitation by avoiding the explicit use of Kohn-Sham orbitals, allowing for larger system sizes and longer simulation time scales. This review introduces the historical contexts, theoretical basis, and challenges of OFDFT, and reviews recent progress and numerical techniques specific to OFDFT. Applications of OFDFT in materials science, chemistry, and physics are also showcased.