Feynman force components: basis for a solution to the covalent vs. ionic dilemma
文献信息
Justyna Dominikowska, Mirosław Jabłoński, Marcin Palusiak
The Hellmann–Feynman theorem, when applied to nuclear coordinates in a molecular system, states that Feynman forces, i.e. forces acting on a nucleus in a molecule, are solely of an electrostatic nature. This theorem is described by Slater as “the most powerful” theorem applicable to molecules. However, its possibilities have hardly been harnessed. This work presents the use of the Hellmann–Feynman theorem in conjunction with the partitioning of the molecular space into atoms in the spirit of the quantum theory of atoms in molecules (QTAIM). Homopolar and heteropolar diatomic molecules of varying polarity are studied in the context of Feynman force components, i.e. the components exerted on each nucleus by the other nucleus and by the electron density distributions of each of the atoms. These results are further related to electronegativity differences used in the differentiation between covalent and ionic bond. The approach based on the directions of Feynman force components gives physical fundamentals for covalent vs. ionic bond distinction without referring to the electronegativity concept.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.












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