Noncovalent Interactions in Density Functional Theory: All the Charge Density We Do Not See
Khabibrakhmanov A, Gori M, Müller C, Tkatchenko A (2025)
Publication Type: Journal article
Publication year: 2025
Journal
Article Number: jacs.5c13706
DOI: 10.1021/jacs.5c13706
Abstract
Exact determination of the electronic density of molecules and materials would provide direct access to accurate bonded and nonbonded interatomic interactions via the Hellman–Feynman theorem. However, density-functional approximations (DFAs)─the workhorse methods for the electronic structure of atomistic systems─only provide approximate and sometimes unreliable electron densities. In this work, we demonstrate that long-range van der Waals (vdW) dispersion interactions can induce significant polarization in the electron density, with the magnitude of effect growing with system size. We evaluate vdW-induced density shifts using newly developed fully coupled and optimally tuned variant of many-body dispersion model (MBD@FCO), benchmarked against accurate coupled-cluster densities. Applied to supramolecular data sets (S12L and L7) and a prototype protein (Fip35-WW), our approach reveals that dispersion-driven polarization alters long-range electrostatic potentials by up to 4 kcal/mol and reshapes noncovalent interaction (NCI) isosurfaces, producing smooth and chemically interpretable interaction regions. These findings demonstrate that dispersion interactions leave a measurable imprint on the electron density, with implications for electrostatics, biomolecular modeling, and density-based chemical analysis. Our results bridge energy-based dispersion models and density-functional theory, paving the way toward dispersion-consistent DFAs and improved machine-learned models based on electron densities.
Authors with CRIS profile
Involved external institutions
Luxembourg (LU)How to cite
APA:
Khabibrakhmanov, A., Gori, M., Müller, C., & Tkatchenko, A. (2025). Noncovalent Interactions in Density Functional Theory: All the Charge Density We Do Not See. Journal of the American Chemical Society. https://doi.org/10.1021/jacs.5c13706
MLA:
Khabibrakhmanov, Almaz, et al. "Noncovalent Interactions in Density Functional Theory: All the Charge Density We Do Not See." Journal of the American Chemical Society (2025).
BibTeX: Download