2019/11/05 by Wenhui Mi, Michele Pavanello
Engineering · Materials Science · Physics and Astronomy · #Ab initio #Advanced Chemical Physics Studies #Algorithm #Benchmark (surveying) #Computer science #Density functional theory #Divide and conquer algorithms #Electron #Kinetic energy #Local-density approximation #Machine Learning in Materials Science #Molecular Junctions and Nanostructures #Orbital-free density functional theory #Physics #Quantum mechanics #Scale (ratio) #Set (abstract data type) #Statistical physics #Work (physics) #cond-mat.mtrl-sci #physics.chem-ph #physics.comp-ph #quant-ph
paper · pdf · doi:10.1021/acs.jpclett.9b03281
arxiv created 2019/11/05 · openalex publication_date 2019/12/10 · arxiv updated 2020/08/24 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/05
electronic structure simulations of molecules and materials. The central ingredient setting subsystem DFT apart from Kohn-Sham DFT is the nonadditive kinetic energy functional (NAKE). Currently employed NAKEs are at most semilocal (i.e., they only depend on the electron density and its gradient), and as a result of this approximation, so far large-scale simulations only included systems composed of weakly interacting subsystems. In this work, we advance the state-of-the-art by introducing fully nonlocal NAKEs in subsystem DFT simulations for the first time. A benchmark analysis based on the S22-5 test set shows that nonlocal NAKEs considerably improve the computed interaction energies and electron densities compared to commonly employed GGA NAKEs, especially when increasing intersubsystem electron density overlap is considered. Most importantly, we resolve the long-standing problem of too attractive interaction energy curves typically resulting from the use of GGA NAKEs.