Chemical Bonding: The Journey from Miniature Hooks to Density Functional Theory

Abstract

Our modern understanding of chemistry is predicated upon bonding interactions between atoms and ions resulting in the assembly of all of the forms of matter that we encounter in our daily life. It was not always so. This review article traces the development of our understanding of bonding from prehistory, through the debates in the 19th century C.E. bearing on valence, to modern quantum chemical models and beyond.

Keywords: affinity, structure; bonding; history of science; valency.

Figure 1

Democritus, together with his mentor Leucippus, are usually credited with the introduction of the atomistic model to Greek philosophy. (Image source, Public Domain, http://www.phil-fak.uni-duesseldorf.de/philo/galerie/antike/demokrit.html).

Figure 2

Bust of Aristotle. Marble, Roman copy after a Greek bronze original by Lysippos from 330 BC; the alabaster mantle is a modern addition (Image source, Public Domain, https://commons.wikimedia.org/wiki/File:Aristotle_Altemps_Inv8575.jpg).

Figure 3

The title page of De rerum natura by Lucretius, from the 1675 edition by Tanaquil Faber. (Image source, Public Domain, https://upload.wikimedia.org/wikipedia/commons/6/6e/Lucretius_De_Rerum_Natura_1675_page_1.jpg).

Figure 4

The title page of the 1661 book The Sceptical Chymist by Robert Boyle, a pioneering work in the history of chemistry that questioned the Greek notions of elements and Aristotelian atomism (Image source, Public Domain, http://www.gutenberg.org/files/22914/22914-h/22914-h.htm).

Figure 5

Geoffroy’s affinity tables represented one of the early attempt to bring order to the wealth of chemical information [84,85,86] (Image source, Public Domain, https://commons.wikimedia.org/wiki/File:Affinity-table.jpg).

Figure 6

Edward Frankland (1825–1899) was the father of valence—or rather “combining power” as he phrased it. (Public domain image taken from https://en.wikipedia.org/wiki/Edward_Frankland).

Figure 7

Friedrich August Kekulé (1829–1896) embraced the valence model and used it to rationalize organic chemistry (Public domain image taken from https://en.wikipedia.org/wiki/August_Kekulé/media/File:Frkekulé.jpg).

Figure 8

(a) John Dalton introduced atomic symbols as a part of his atomic model and (b) anticipated the occurrence of isomers in which atoms were arranged in different spatial manners (1829–1896) embraced the valence model and used it to rationalize organic chemistry [113,114,115]. (Image taken from https://www.biodiversitylibrary.org/bibliography/9535).

Figure 9

Sir Joseph John Thomson (1856–1940), the discoverer of the electron. Once the electron had been discovered, the time was ripe for modern theories of bonding to emerge. (Public domain image taken from https://en.wikipedia.org/wiki/J._J._Thomson#/media/File:J.J_Thomson.jpg).

Figure 10

The credit for the development of the modern conceptual models of bonding goes to (a) Gilbert Newton Lewis (1875–1946) who placed electrons to be shared at the vertices of a cube (thus conforming to the octet model) and (b) Walther Ludwig Julius Kossel (1888–1956) who considered the complete transfer of electrons in ionic bonds. (Images taken from https://en.wikipedia.org/wiki/Gilbert_N._Lewis#/media/File:Lewis-cubic-notes.jpg and https://en.wikipedia.org/wiki/Walther_Kossel#/media/File:Kossel,Walther_1928.jpg).

Figure 11

Linus Carl Pauling (1901–1994) probably did more to transform the understanding of bonding than any other scientist and the legacy of his paradigm-shift book The Nature of the Chemical Bond lives on today. (Public domain images taken from https://en.wikipedia.org/wiki/Linus_Pauling#/media/File:Linus_Pauling_1948.png).