A Quantum Chemical Topology Picture of Intermolecular Electrostatic Interactions and Charge Penetration Energy

23 June 2021, Version 2
This content is a preprint and has not undergone peer review at the time of posting.


Basing on the interacting quantum atoms approach, we present a conceptual and theoretical framework of short-range electrostatic interactions, whose accurate description is still a challenging problem in molecular modeling. For all the non-covalent complexes in the S66 database, the fragment and atomic decomposition of the electrostatic binding energies is performed using both the charge density of the dimers and the unrelaxed densities of the monomers. This energy decomposition together with dispersion corrections gives rise to a pairwise approximation to the total binding energy. It also provides energetic descriptors at varying distance that directly address the atomic and molecular electrostatic interactions as described by point-charge or multipole-based potentials. Additionally, we propose a consistent definition of the charge penetration energy within quantum chemical topology, which is mainly characterized in terms of the intramolecular electrostatic energy. Finally, we discuss some practical implications of our results for the design and validation of electrostatic potentials.


Molecular Modeling
Electrostatic interactions
charge penetration correction
Quantum Chemical Topology
Interacting Quantum Atoms

Supplementary materials

QCT Elec Analysis ChemRxiv SI
Supporting Information


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