Abstract
Two different models for chemical bond were developed almost simultaneously after the Schrödinger formulation of quantum theory. These are known as the valence bond (VB) and molecular orbital (MO) theories. Initially chemists preferred the VB theory and ignored the MO theory. Now the VB theory is almost dropped out of currency. The context of discovery and Linus Pauling’s overpowering influence gave the VB theory its initial advantage. The current universal acceptance of the MO theory is due to its ability to provide direct interpretation of many different types of experiments now being pursued. In current research both localized bonds and delocalized charge distributions play important roles and the MO theory has been successful in giving a good account of both.
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Notes
A wave function for hydrogen molecule developed by Coulson and Fisher has both VB and MO features (Coulson and McWeeny 1979).
See Berson (1999) for detailed discussion. J. Murdoch (personal communication) gives a detailed history on this topic.
The article is available in translation (Hettema 2000, pp. 140–156). Hettema’s book also has many classic papers in quantum theory with an insightful preface.
Spin and normalization constants are not shown since they are not relevant to discussion.
The article is available in translation (Hettema 2000, pp. 214–235).
I have not been able to read Øyvind Burrau’s article either in the original or in translation. An excellent account, however, with all the details is given in Pauling and Wilson (1963, pp. 332–340).
See Pauling’s treatment of Ferrocene on pages 385–392. Even though the MO treatment is very much simpler and leads to understanding of many properties, he barely mentions it. Instead he describes the VB treatment which calls for 560 terms in the wave function just to get a rough estimate of the bond lengths.
The qualitative prediction that delocalization (which is related to the width of the wave packet) lowers energy is independent of any approximations in quantum calculations. See particle in a box example discussed in almost every book on quantum.
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Acknowledgment
I am indebted to Carolyn Vemulapalli for editorial assistance and helpful suggestions and to Dr. J. Murdoch for very useful discussions. I thank the two reviewers for carefully reading and suggesting improvements and also for pointing out the ambiguities in the text sent for review.
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Vemulapalli, G.K. Theories of the chemical bond and its true nature. Found Chem 10, 167–176 (2008). https://doi.org/10.1007/s10698-008-9049-2
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DOI: https://doi.org/10.1007/s10698-008-9049-2