Advertisement

Foundations of Chemistry

, Volume 10, Issue 3, pp 147–156 | Cite as

Fundamental theories and their empirical patches

  • Jerome A. BersonEmail author
Article

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.

Keywords

Merit of theories Empirical content Pragmatic imperatives 

Notes

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.

References

  1. Berry, M., Robbins, J.: Quantum indistinguishability: spin-statistics without relativity or field theory. In: Hilborn, R.C., Tino, G.M. (eds.) Spin Statistics Connection and Commutation Relations, vol. 545, pp. 3–15. AIP Conference Proceedings. AIP, Melville, NY (2000)Google Scholar
  2. Berson J.A.: Chemical Discovery and the Logicians’ Program. A Problematic Pairing. Wiley-VCH, Weinheim, Germany (2003)Google Scholar
  3. Berson J.A.: Kinetics thermodynamics, the problem of selectivity the maturation of an idea. A review. Angew. Chem. 45, 4724–4729 (2006)CrossRefGoogle Scholar
  4. Blowers, P., Masel, R.I.: An extension of the Marcus equation for atom transfer reactions. J. Phys. Chem. 103, 7047–7054 (1999)Google Scholar
  5. Borden, W.T.: The partnership between electronic structure calculations and experiments in the study of reactive intermediates, pp. 961–1004. In: Moss, R.A., Platz, M.S., Jr. Jones, M. (eds.) Reactive Intermediate Chemistry. Wiley-Interscience, New York, NY (2004)Google Scholar
  6. Carpenter B.K.: Potential energy surfaces and reaction dynamics. In: Moss R.A., Platz M.S., Jr Jones M., (eds.) Reactive Intermediate Chemistry, pp. 925–960. Wiley-Interscience, New York, NY (2004)Google Scholar
  7. Cramer C.J.: Essentials of Computational Chemistry. John Wiley, New York, NY (2002)Google Scholar
  8. da Costa N.C.A., French S.: Science, Partial Truth: A Unitary Approach to Models and Scientific Reasoning. Oxford University Press, Oxford (2003)Google Scholar
  9. Dirac, P.A.M.: The quantum theory of the electron. Proc. Roy. Soc. (London) A112, 610–624 (1926) Google Scholar
  10. Duck I., Sudarshan E.C.G.: Pauli and the Spin-Statistics Theorem. World Scientific, Singapore; River Edge, NJ (1997a)Google Scholar
  11. Duck I., Sudarshan E.C.G.: Toward an understanding of the spin statistics theorem. Am. J. Phys. 66, 284–303 (1997b) CrossRefGoogle Scholar
  12. French, S.: Putting a new spin on particle identity. In: Hilborn, R.C., Tino, G.M. (eds.): Spin Statistics and Commutation Relations: Experimental Tests and Theoretical Implications, pp. 305–318. American Institute of Physics, Melville, NY. Proceedings of a conference held in Anacapri, Capri Island, Italy (2000)Google Scholar
  13. Gero, A.: Kekulé’s theory of aromaticity. J. Chem. Ed. 31, 201–202 (1954) CrossRefGoogle Scholar
  14. Heisenberg, W.: The spectra of atomic systems with two electrons. Z. Physik. 39, 499–518 (1926) CrossRefGoogle Scholar
  15. Hilborn, R.C., Tino, G.M. (eds.) Spin Statistics and Commutation Relations: Experimental Tests and Theoretical Implications. American Institute of Physics, Melville, NY (2000). Proceedings of a conference held in Anacapri, Capri Island, Italy (2000a)Google Scholar
  16. Hilborn, R.C., Tino, G.M.: Preface. In: Hilborn, R.C., Tino, G.M. (eds.) Spin Statistics and Commutation Relations: Experimental Tests and Theoretical Implications, ix. American Institute of Physics, Melville, NY (2000b)Google Scholar
  17. Hilborn, R.C., Tino, G.M.: Several of the contributions, by the way, reported deliberate but unsuccessful experimental attempts to violate the Pauli Principle by forcing a third electron into a doubly occupied atomic orbital (2000c)Google Scholar
  18. Ihde A.J.: The Development of Modern Chemistry. Dover, New York (1964)Google Scholar
  19. Kaplan, I.G.: Pauli spin statistics theorem and statistics of quasiparticles in a periodical lattice. In: Hilborn, R.C., Tino, G.M. (eds.) Spin Statistics and Commutation Relations: Experimental Tests and Theoretical Implications, pp. 72–78. American Institute of Physics, Melville, NY. Proceedings of a conference held in Anacapri, Capri Island, Italy (2000)Google Scholar
  20. Kaplan, I.G.: Is the Pauli exclusive principle an independent quantum mechanical postulate? Intl. J. Quantum Chem. 89, 268–276 (2002) CrossRefGoogle Scholar
  21. Laudan L.: Science and Hypothesis. Historical Essays on Scientific Methodology. D. Reidel, Dordrecht, Holland (1981)Google Scholar
  22. Marcus, R.A.: The theory of oxidation–reduction reactions involving electron transfer. I. J. Chem. Phys. 24, 966–978 (1956) CrossRefGoogle Scholar
  23. Marcus, R.A.: Theory of electron-transfer reactions. VI. Unified treatment for homogeneous and electrode reactions. J. Chem. Phys. 43, 679–701 (1965) CrossRefGoogle Scholar
  24. Marcus, R.A.: Theoretical relations among rate constants, barriers, and Brönsted slopes of chemical reactions. J. Phys. Chem. 72, 891–899 (1968) CrossRefGoogle Scholar
  25. Marcus, R.M.: A comment on the lecture by J.R. Murdoch. Faraday Soc. Disc. Chem. Soc. 74, 307 (1982) Google Scholar
  26. Massimi M.: Pauli’s Exclusion Principle: The Origin and Validation of a Scientific Principle. Cambridge University Press, Cambridge/New York (2005)Google Scholar
  27. Pauli, W.: The relation between the completion of the electron groups of the atom and the complex structure of the spectra. Z. Phys. 31, 765–783 (1925) CrossRefGoogle Scholar
  28. Pauli, W.: The connection between spin and statistics. Phys. Rev. 58, 716–722 (1940) CrossRefGoogle Scholar
  29. Pauli, W.: Exclusion principle and quantum mechanics. Nobel Lectures, Physics, 1942–1962, Elsevier Publishing Company, Amsterdam, pp. 27–43 (1964)Google Scholar
  30. Scerri E.R.: Lowdin’s remarks on the Aufbau principle and a philosopher’s view of ab initio quantum chemistry. In: Brändas E.J., Kryachko E.S. (eds.) Fundamental World of Quantum Chemistry, 675 pp. Kluwer Academic, Dordrecht, Netherlands (2003)Google Scholar
  31. Shaik, S.: The collage of SN2 reactivity patterns. A state correlation diagram model. Progr. Phys. Org. Chem. 15, 214–215, 224–230 (1985) Google Scholar
  32. Slater, J.C.: Quantum Theory of Atomic Structure, pp. 282–285. McGraw-Hill, New York, NY (1960) Google Scholar
  33. Sudarshan E.C.G.: Pauli spin statistics theorem and statistics of quasiparticles in a periodical lattice. In: Hilborn R.C., Tino G.M. (eds.) Spin Statistics and Commutation Relations: Experimental Tests and Theoretical Implications, pp. 40–54. American Institute of Physics, Melville, NY (2000)Google Scholar
  34. Uhlenbeck, G.E., Goudsmit, S.: Ersetzung der Hypothese vom unmechanischen Zwang durch eine Forderung bezüglich des inneren Verhaltens jedes einzelnen Elektrons. Die Naturwissenschaften 13, 953–954 (1925)CrossRefGoogle Scholar
  35. Uhlenbeck, G.E., Goudsmit, S.: Spinning electrons and the structure of spectra. Nature 117, 264–265 (1926) CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V. 2008

Authors and Affiliations

  1. 1.Department of ChemistryYale UniversityNew HavenUSA

Personalised recommendations