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<p>A comprehensive quantum chemical topology perspective based on electronic force fields is developed to describe the chemical structure and evolution of many-electron multinuclear systems. This methodology, grounded in the superposition of conservative electronic force fields—namely, the electrostatic, exchange, and total static force densities—establishes a rigorous quantum–mechanical framework for elucidating interatomic interactions and internuclear binding within the theory of pseudoatoms in molecules. The superimposed topological portraits of these force fields reveal distinct binding modes, offering an alternative interpretation of chemical bonding that transcends traditional orbital-based paradigms. Notably, the fusion of nonnuclear exchange-force-field basins is identified as a manifestation of a topological catastrophe, demarcating the transition from a more covalent to a less covalent interatomic interaction regime. The quantification of the partial electrostatic-force and exchange-force contributions to the total static force, combined with the analysis of the exchange charge density and the Laplacian of the electron density, reveals how the classical Coulomb interelectronic interaction and the nonclassical Fermi correlation in electron motion manifest themselves in physical space—most notably within the superimposed topology of the electronic force fields. Moreover, the fundamental charge constraints, imposed by the corresponding zero-flux conditions, for the closed basins defined within the specified force fields are derived from the Ostrogradsky–Gauss divergence theorem and Poisson’s equation, marking a major advancement in the understanding of atomic charge redistribution. Furthermore, the rigorous formulations of the integral fluxes of the electrostatic force and the exchange force through the internal turning surface, defined within the total static force field, are presented. These findings underscore the pivotal role of the electronic force density analysis in delineating atomic domains, characterizing chemical bonds, and elucidating interatomic charge transfer, electron-transfer-induced quantum chemical response, and electron sharing mechanisms.</p>

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Chemical structure and its evolution in terms of the superimposed electrostatic, exchange, and total static force fields, and the role of the electronic forces in atomic charge redistribution

  • 期刊论文

  • 发表日期：

    2025年6月28日

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  • Sergey V. Kartashov,
  • Robert R. Fayzullin

摘要

A comprehensive quantum chemical topology perspective based on electronic force fields is developed to describe the chemical structure and evolution of many-electron multinuclear systems. This methodology, grounded in the superposition of conservative electronic force fields—namely, the electrostatic, exchange, and total static force densities—establishes a rigorous quantum–mechanical framework for elucidating interatomic interactions and internuclear binding within the theory of pseudoatoms in molecules. The superimposed topological portraits of these force fields reveal distinct binding modes, offering an alternative interpretation of chemical bonding that transcends traditional orbital-based paradigms. Notably, the fusion of nonnuclear exchange-force-field basins is identified as a manifestation of a topological catastrophe, demarcating the transition from a more covalent to a less covalent interatomic interaction regime. The quantification of the partial electrostatic-force and exchange-force contributions to the total static force, combined with the analysis of the exchange charge density and the Laplacian of the electron density, reveals how the classical Coulomb interelectronic interaction and the nonclassical Fermi correlation in electron motion manifest themselves in physical space—most notably within the superimposed topology of the electronic force fields. Moreover, the fundamental charge constraints, imposed by the corresponding zero-flux conditions, for the closed basins defined within the specified force fields are derived from the Ostrogradsky–Gauss divergence theorem and Poisson’s equation, marking a major advancement in the understanding of atomic charge redistribution. Furthermore, the rigorous formulations of the integral fluxes of the electrostatic force and the exchange force through the internal turning surface, defined within the total static force field, are presented. These findings underscore the pivotal role of the electronic force density analysis in delineating atomic domains, characterizing chemical bonds, and elucidating interatomic charge transfer, electron-transfer-induced quantum chemical response, and electron sharing mechanisms.