Foundations of Chemistry

, Volume 14, Issue 3, pp 235–243 | Cite as

A neglected aspect of the puzzle of chemical structure: how history helps



Intra-molecular connectivity (that is, chemical structure) does not emerge from computations based on fundamental quantum-mechanical principles. In order to compute molecular electronic energies (of C3H4 hydrocarbons, for instance) quantum chemists must insert intra-molecular connectivity “by hand.” Some take this as an indication that chemistry cannot be reduced to physics: others consider it as evidence that quantum chemistry needs new logical foundations. Such discussions are generally synchronic rather than diachronic—that is, they neglect ‘historical’ aspects. However, systems of interest to chemists generally are metastable. In many cases chemical systems of a given elemental composition may exist in any one of several different metastable states depending on the history of the system. Molecular structure generally depends on contingent historical circumstances of synthesis and separation, rather than solely or mainly on relative energies of alternative stable states, those energies in turn determined by relationships among components. Chemical structure is usually ‘kinetically-determined’ rather than ‘thermodynamically-determined.’ For instance, cyclical hydrocarbon ring-systems (as in cyclopropene) are produced only in special circumstances. Adequate theoretical treatments must take account of the persistent effects of such contingent historical events whenever they are relevant—as they generally are in chemistry.


Synchronic Diachronic Isomers Chemical structure W*-algebra Allene Propyne Propadiene Philosophy of chemistry Metastable Potential energy surfaces Equilibrium states Transition states Quantum chemistry Historicity Contextual emergence 



A research grant from the Graduate School of Georgetown University is gratefully acknowledged.


  1. Basolo, F., Pearson, R.G.: Mechanisms of Inorganic Reactions; a Study of Metal Complexes in Solution, 2nd edn. Wiley, New York (1967)Google Scholar
  2. Bishop, R.C.: Patching physics and chemistry together. Philos. Sci. 72, 716–722 (2005)CrossRefGoogle Scholar
  3. Bishop, R.C., Atmanspacher, H.: Contextual emergence in the description of properties. Found. Phys. 36, 1753–1777 (2006)CrossRefGoogle Scholar
  4. Chalmers, A.: The Scientist’s Atom and the Philosopher’s Stone: How Science Succeeded and Philosophy Failed to Gain Knowledge of Atoms (Boston Studies in the Philosophy of Science, v. 279). Springer, Dordrecht (2009)Google Scholar
  5. Czakó, G., Bowman, J.M.: Dynamics of the reaction of methane with chlorine atom on an accurate potential energy surface. Science 334, 343–346 (2011)CrossRefGoogle Scholar
  6. Hendry, R.F.: Ontological reduction and molecular structure. Stud. Hist. Philos. Mod. Phys. 41, 183–191 (2010)CrossRefGoogle Scholar
  7. Hirst, J.: Why does mitochondrial complex I have so many subunits? Biochem. J. 437, e1–e3 (2011)CrossRefGoogle Scholar
  8. Humphreys, P.: Synchronic and diachronic emergence. Mind. Mach. 18, 431–442 (2008)CrossRefGoogle Scholar
  9. Kauffman, Stuart.A.: The Origins of Order: Self-Organization and Selection in Evolution. Oxford University Press, New York (1993). (Chapter 3)Google Scholar
  10. Kim, J.: Physicalism, or Something Near Enough. Princeton University Press, Princeton (2005)Google Scholar
  11. Leigh, W.J.: Techniques and applications of Far-UV photochemistry in solutions: the photochemistry of the C3H4 and C4H6 hydrocarbons. Chem. Rev. 93, 487–505 (1993)CrossRefGoogle Scholar
  12. Lebedev, V.L., Bagatur’yants, A.A., Taber, A.M., Kalechits, I.V.: Quantum-chemical study of isomerization in the allene-methylacetylene-cyclopropene system. Russ. Chem. Bull. 28(3), 452–457 (1979). (Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya,No.3, pp. 491–496, March, 1979.)Google Scholar
  13. Maeda, S., Ohno, K.: Global mapping of equilibrium and transition structures on potential energy surfaces by the scaled hypersphere search method: applications to ab initio surfaces of formaldehyde and propyne molecules. J. Phys. Chem. A 109, 5742–5753 (2005)CrossRefGoogle Scholar
  14. Mebel, M., Jackson, W.M., Chang, A.H.H., Lin, S.H.: Photodissociation dynamics of propyne and allene: a view from ab initio calculations of the C3Hn (n = 1–4) species and the isomerization mechanism for C3H2. J. Am. Chem. Soc. 120, 5751–5763 (1998)CrossRefGoogle Scholar
  15. Primas, H.: Chemistry, Quantum Mechanics, and Reductionism. Springer, Berlin (1983)CrossRefGoogle Scholar
  16. Roca, M., Liu, H., Messer, B., Warshell, A.: On the relationship between thermal stability and catalytic power of enzymes. Biochemistry 46, 15076–15088 (2007)CrossRefGoogle Scholar
  17. Scerri, E.R.: Editorial 37. Found. Chem. 13, 1–7 (2011)CrossRefGoogle Scholar
  18. Schlatter, M.J.: The preparation of cyclopropene. J. Am. Chem. Soc. 63, 1733–1737 (1941)CrossRefGoogle Scholar
  19. Slutsky, D.: Confusion and dependence in the uses of history. Synthese 184, 261–286 (2012)Google Scholar
  20. Sutcliff, B.T., Woolley, R.G.: A comment on editorial 37. Found. Chem. 13, 93–96 (2011)CrossRefGoogle Scholar
  21. Su, M.-d.: Photochemical isomerization reactions of cyclopropene and 1,3,3, trimethylcyclopropene: a theoretical study. J. Chem. Theory Comput. 4, 1263–1273 (2008)CrossRefGoogle Scholar
  22. Wooley, R.G.: Is there a quantum definition of a molecule? J. Math. Chem. 23, 3–11 (1998)CrossRefGoogle Scholar

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© Springer Science+Business Media B.V. 2012

Authors and Affiliations

  1. 1.Department of ChemistryGeorgetown UniversityFalls ChurchUSA

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