Subsystem density‐functional theory

Abstract

Subsystem density‐functional theory (subsystem DFT) has developed into a powerful alternative to Kohn–Sham DFT for quantum chemical calculations of complex systems. It exploits the idea of representing the total electron density as a sum of subsystem densities. The optimum total density is found by minimizing the total energy with respect to each of the subsystem densities, which breaks down the electronic‐structure problem into effective subsystem problems. This enables calculations on large molecular aggregates and even (bio‐)polymers without system‐specific parameterizations. We provide a concise review of the underlying theory, typical approximations, and embedding approaches related to subsystem DFT such as frozen‐density embedding (FDE). Moreover, we discuss extensions and applications of subsystem DFT and FDE to molecular property calculations, excited states, and wave function in DFT embedding methods. Furthermore, we outline recent developments for reconstruction techniques of embedding potentials arising in subsystem DFT, and for using subsystem DFT to incorporate constraints into DFT calculations. This article is categorized under:Structure and Mechanism > Computational Materials Science