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The Lewis electron-pair bonding model: the physical background, one century later

Nature Reviews Chemistry volume 3, pages 35–47 (2019)Cite this article

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Abstract

The shared electron-pair bonding model was suggested by Gilbert Lewis more than 100 years ago. Emerging from the chemical experience of the time, Lewis structures described contemporary aspects of chemical reality in terms of empirically adapted models without any (then unknown) quantum physical underpinnings. This Perspective details the origins and historical development of the Lewis model, which we contrast with the physical understanding of chemical bonding in terms of contemporary quantum chemistry. Some intuitively plausible classical explanations of the past, not least of which are the sharing of electrons by two atoms and the subtypes of shared electron-pair bonding and dative bonding, turned out to be well founded. Some other chemical dogmata, including the concept that bonding occurs only between two nuclei and is caused by spin coupling or that bond energy is of purely electrostatic origin, are less well founded. We now know that covalent bonding is not driven by the formation of an electron pair but rather by the lowering of the kinetic energy density of the shared electrons in the bonding region, which is provided by the interference of the atomic wavefunctions. Lewis structures remain highly useful models for describing chemical bonding in molecular structures and chemical reactions, particularly when supported by quantum chemistry. The concepts behind the three most common quantum chemical approximations — the valence bond, molecular orbital and density functional theories — are described. These methods allow us to learn that bonding is an energetic phenomenon, from which descriptors such as bond length, bond dissociation energies and force constants are derivable. The energetic origins of bonding point to bond energy decomposition analysis as a natural tool for elucidating the actions of bonding electrons.

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Fig. 1: Gilbert Lewis suggested visualizing atoms as cubes, at the vertices of which lie spheres representing electrons.
Fig. 2: The annual citations of Gilbert Lewis’ paper The atom and the molecule since its publication in 1916.
Fig. 3: A portrait of Gilbert Lewis.
Fig. 4: Heitler and London calculated the energy of H2 as a function of internuclear separation.
Fig. 5: Plot of the energy of H2 versus internuclear separation.

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Acknowledgements

G.F. and L.Z. acknowledge financial support from Nanjing Tech University (grant nos 39837132 and 39837123) and a SICAM Fellowship from Jiangsu National Synergetic Innovation Center for Advanced Materials. L.Z. also acknowledges financial support from the Natural Science Foundation of Jiangsu Province for Youth (grant no. BK20170964) and the National Natural Science Foundation of China (grant no. 21703099). W.H.E.S. thanks J. Li and the Theoretical & Computational Chemistry Laboratory at Tsinghua University.

Author information

Authors and Affiliations

  1. Institute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Jiangsu National Synergetic Innovation Center for Advanced Materials, Nanjing Tech University, Nanjing, China

    Lili Zhao & Gernot Frenking

  2. Theoretical Chemistry Center, Tsinghua University, Beijing, China

    W. H. Eugen Schwarz

  3. Physical and Theoretical Chemistry Group, Universität Siegen, Siegen, Germany

    W. H. Eugen Schwarz

  4. Fachbereich Chemie, Philipps-Universität Marburg, Marburg, Germany

    Gernot Frenking

  5. Donostia International Physics Center, Donostia–San Sebastián, Spain

    Gernot Frenking

Authors
  1. Lili Zhao
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  2. W. H. Eugen Schwarz
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  3. Gernot Frenking
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All authors contributed equally to the preparation of this manuscript.

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Correspondence to W. H. Eugen Schwarz or Gernot Frenking.

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Zhao, L., Schwarz, W.H.E. & Frenking, G. The Lewis electron-pair bonding model: the physical background, one century later. Nat Rev Chem 3, 35–47 (2019). https://doi.org/10.1038/s41570-018-0052-4

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