Developing Quantum Chemical Topology for Polypeptide Charge Distributions Using Kohn-Sham One-electron Potential

Abstract

We introduce a quantum chemical topology (QCT) approach using the Kohn-Sham one-electron potential (KSpot) as a scalar function, revealing unique spatial features of atoms in molecules and the chemical bonds. The KSpot and its electron force lines demonstrate that an atom is a 3D basin governed by its nucleus as an attractor. Notably, KSpot atomic charges exhibit less basis set dependence, whose physical reliability is further confirmed through accurate reproduction of electrostatic potentials and dipole moments. To assess performance, we systematically compared KSpot QCT atomic charges with six established methods (QTAIM, Hirshfeld, Mülliken, NPA, CHELPG, and MK) across 20 amino acid dipeptides. KSpot charges have strong correlations with QTAIM and Hirshfeld ones, with correlation coefficients of 0.9207 and 0.9160, respectively. Furthermore, we successfully parameterized the atom bond electronegativity equalization method (ABEEM) using KSpot QCT charges, achieving a good linear agreement between them. These results establish KSpot QCT as a robust tool for molecular structure analysis, electrostatic interaction studies, and force field development.

Keywords

Kohn-Sham one-electron potential (KSpot) / Quantum chemical topology (QCT) / Atomic charge / Polypeptide / Atom-bond electronegativity equalization method

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