Abstract
Many theories require empirical patches or ad hoc assumptions to work properly in application to chemistry. Some examples include the Bohr quantum theory of atomic spectra, the Pauli exclusion principle, the Marcus theory of the rate-equilibrium correlation, Kekule’s hypothesis of bond oscillation in benzene, and the quantum calculation of reaction pathways. Often the proposed refinements do not grow out of the original theory but are devised and added ad hoc. This brings into question the goal of constructing theories derived from first principles and the concept of ranking the merit of theories according to their freedom from empirical contamination.
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Acknowledgments
I thank D.M. Birney, J.R. Murdoch, and J.C. Tully for helpful discussions of the rate-equilibrium relationship. F.R. Firk, F. Iachello, and C.M. Sommerfield made instructive comments on special relativity and the spin-statistics connection. Responsibility for the statements here, however, rests solely with the author.
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Berson, J.A. Fundamental theories and their empirical patches. Found Chem 10, 147–156 (2008). https://doi.org/10.1007/s10698-008-9046-5
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DOI: https://doi.org/10.1007/s10698-008-9046-5