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XI.—Quantum Theory of the Chemical Bond

Published online by Cambridge University Press:  14 February 2012

C. A. Coulson
C. A. Coulson
Affiliation:
University College, Dundee
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Summary

Wave mechanics is able to describe with some precision the motions of electrons in atoms, but when we study molecules we have to use more approximate descriptions. It turns out that what the chemist is accustomed to call a single bond is in reality a pair of electrons, having opposed spins, describing equivalent orbits which have symmetry about the line joining the two nuclei concerned; this may be called a localised bond. The tetrahedral character of the bonds from saturated Carbon atoms are easily fitted into this scheme.

In Ethylene, however, another type of orbit appears; this is the double-streamer orbit, and two electrons in this orbit convert a normal single bond into a double bond. Again the bond is a localised bond, with a characteristic energy and length.

In more complex molecules, such as Benzene, there is a framework of single bonds, and the remaining electrons have orbits that embrace all six of the Carbon atoms; these mobile electrons give the aromatic and conjugated molecules their characteristic properties, but as a result the bonds are neither pure single bonds nor pure double bonds, but a hybrid of the two, and the electrons in these bonds are no longer localised in the region between any two particular nuclei. The energies of these molecules can be calculated in fair agreement with experiment, and from a knowledge of the wave function it is possible to define an order, which is usually fractional, for these bonds. In Benzene all the C-C links are equivalent, and their order is I⅔.

A curve which connects the fractional order with the length of the bond enables us to predict the lengths of these bonds, and, where experimental comparison is available, agreement is found. These mobile electrons are important in a study of vibration frequencies, restricted rotation about C-C bonds, and in polymerisation.

Type
Research Article
Information
Proceedings of the Royal Society of Edinburgh Section A: Mathematics , Volume 61 , Issue 2 , 1942 , pp. 115 - 139
Copyright
Copyright © Royal Society of Edinburgh 1942

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References

References to Literature

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