Lewis, Paul

Harris, M. 2008. Chemical reductionism revisited Lewis, Pauling, and the physico-chemical nature of the chemical bond. Studies in History and Philosophy of Science 39 78-90. 

Lewis, as a physicist, was also well aware of early developments we ve come to call Quantum Theory, but his most outspoken concerns for what impact this might have on chemistry from 1916 and 1923 preceded the mathematical developments of both Schrodinger and Heisenberg. It is of interest to note, however, that Linus Pauling who authored the first major text for the new quantum chemistry. The Nature of the Chemical Bond, dedicated this work to G. N. Lewis. Pauling s major text of 1939 was subtitled An Introduction to Structural Chemistry , and the fundamental principle, he declares, is this ... 

The increased-valence theory represents a natural extension of the more familiar Lewis-Pauling valence-bond theory. Therefore an understanding of it may be useful for all chemists who have an interest in qualitative valence-bond descriptions of electronic structure. It will be shown that all Lewis-type valence-bond structures with lone-pairs of electrons can be stabilized easily via one-electron delocalizations from doubly-occupied atomic orbitals into diatomic bonding molecular orbitals when the relevant atomic orbitals overlap, as is shown here for the two sets of oxygen n electrons of N2O. 

It is possible to write a simple Lewis structure for foe S042- ion, involving only single bonds, which follows foe octet rule. However, Linus Pauling and others have suggested an alternative structure, involving double bonds, in which foe sulfur atom is surrounded by six electron pairs. 

Linus Pauling, Proc. Nat. Acad. Set., 18, 293 (1932). Examples of molecules which resonate among several Lewis structures are given in this paper. Further discussion of the nitrous oxide molecule is given in a later note, Linus Pauling, ibid., July, 1932. 

Lewis, T. W. Curtin, D. Y. Paul, I. C. Thermal, photochemical and photonucleated thermal dehydration of /j-hydroxytriary I methanols in the solid state. (3,5-Dimethyl-4-hydroxyphenyl)diphenyl methanol and (3,5-dibromo-4-hyrdoxyphenyl)di phenyl methanol X-ray crystallography of (4-hydroxyphenyl)diphenyl methanol and its 3,5-dimethyl derivative. J. Am. Chem. Soc. 1979, 101, 5717-5725. 

Also during the 1970s, research on the role of H in amorphous semiconductors intensified rapidly. Paul and coworkers (Lewis et al., 1974 Paul et al., 1976) were the first to recognize that H had a role in improving the properties of amorphous semiconductors. But what triggered the... 

G. N. Lewis, J. Am. Chem. Soc. 38 (1916), 762 G. N. Lewis, Valence and the Structure of Atoms and Molecules (New York, The Chemical Catalog Co., 1923). As observed by Pauling (in note 51, p. 5), this remarkable work forms the basis of the modern electronic theory of valence. ... 

Soon after the quantum revolution of the mid 1920s, Linus Pauling and John C. Slater expanded Lewis s localized electronic-structural concepts with the introduction of directed covalency in which bond directionality was achieved by the hybridization of atomic orbitals.1 For normal and hypovalent molecules, Pauling and Slater proposed that sp" hybrid orbitals are involved in forming shared-electron-pair bonds. Time has proven this proposal to be remarkably robust, as has been demonstrated by many examples in Chapter 3. 

Resonance such as (5.28a)-(5.28c) is inherently a quantal phenomenon, with no classical counterpart. In NBO language, each of the resonance interactions (5.28a)-(5.28c) corresponds to a donor-acceptor interaction between a nominally filled (donor Lewis-type) and unfilled (acceptor non-Lewis-type) orbital, the orbital counterpart of G. N. Lewis s general acid-base concept. As mentioned above, Lewis and Werner (among others) had well recognized the presence of such valence-like forces in the dative or coordinative binding of free molecular species. Thus, the advent of quantum mechanics and Pauling s resonance theory served to secure and justify chemical concepts that had previously been established on the basis of compelling chemical evidence. 

This graduate-level text presents the first comprehensive overview of modern chemical valency and bonding theory, written by internationally recognized experts in the held. The authors build on the foundation of Lewis- and Pauling-like localized structural and hybridization concepts to present a book that is directly based on current ab initio computational technology. 

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