Open AccessA Quantum Chemical Topology Picture of Intermolecular Electrostatic Interactions and Charge Penetration Energy
Author(s) -
Fernando JiménezGrávalos,
Dimas Suárez
Publication year - 2021
Publication title -
journal of chemical theory and computation
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.001
H-Index - 185
eISSN - 1549-9626
pISSN - 1549-9618
DOI - 10.1021/acs.jctc.1c00263
Subject(s) - electrostatics , multipole expansion , electric potential energy , intermolecular force , chemical physics , intramolecular force , interaction energy , quantum , quantum chemistry , physics , binding energy , non covalent interactions , topology (electrical circuits) , chemistry , computational chemistry , atomic physics , molecule , quantum mechanics , energy (signal processing) , hydrogen bond , supramolecular chemistry , mathematics , combinatorics
Based on the Interacting Quantum Atoms approach, we present herein a conceptual and theoretical framework of short-range electrostatic interactions, whose accurate description is still a challenging problem in molecular modeling. For all the noncovalent complexes in the S66 database, the fragment-based 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.