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

doi:10.1007/s40242-025-5150-5

高等学校化学研究 ›› 2025, Vol. 41 ›› Issue (5): 1121-1132.doi: 10.1007/s40242-025-5150-5

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

GUO Xin, CONG Yunhong, ZHAO Jian, ZHAO Dongxia, YANG Zhongzhi

School of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, P. R. China

收稿日期:2025-07-15 接受日期:2025-08-30 出版日期:2025-10-01 发布日期:2025-09-26
通讯作者: ZHAO Jian, E-mail: zhaoj2333@lnnu.edu.cn;ZHAO Dongxia, E-mail: zhaodxchem@lnnu.edu.cn;YANG Zhongzhi, E-mail: zzyang@lnnu.edu.cn E-mail:zhaoj2333@lnnu.edu.cn;zhaodxchem@lnnu.edu.cn;zzyang@lnnu.edu.cn
基金资助:
This work was supported the National Natural Science Foundation of China (Nos. 22273033 and 22402188).

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

GUO Xin, CONG Yunhong, ZHAO Jian, ZHAO Dongxia, YANG Zhongzhi

School of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, P. R. China

Received:2025-07-15 Accepted:2025-08-30 Online:2025-10-01 Published:2025-09-26
Contact: ZHAO Jian, E-mail: zhaoj2333@lnnu.edu.cn;ZHAO Dongxia, E-mail: zhaodxchem@lnnu.edu.cn;YANG Zhongzhi, E-mail: zzyang@lnnu.edu.cn E-mail:zhaoj2333@lnnu.edu.cn;zhaodxchem@lnnu.edu.cn;zzyang@lnnu.edu.cn
Supported by:
This work was supported the National Natural Science Foundation of China (Nos. 22273033 and 22402188).

摘要/Abstract

摘要： 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.

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

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.

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

GUO Xin, CONG Yunhong, ZHAO Jian, ZHAO Dongxia, YANG Zhongzhi. Developing Quantum Chemical Topology for Polypeptide Charge Distributions Using Kohn-Sham One-electron Potential[J]. 高等学校化学研究, 2025, 41(5): 1121-1132.

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

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

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