Understanding the Woodward–Hoffmann Rules by Using Changes in Electron Density Academic Article uri icon

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abstract

  • The Woodward-Hoffmann rules for pericyclic reactions are explained entirely in terms of directly observable physical properties of molecules (specifically changes in electron density) without any recourse to model-dependent concepts, such as orbitals and aromaticity. This results in a fundamental explanation of how the physics of molecular interactions gives rise to the chemistry of pericyclic reactions. This construction removes one of the key outstanding problems in the qualitative density-functional theory of chemical reactivity (the so-called conceptual DFT). One innovation in this paper is that the link between molecular-orbital theory and conceptual DFT is treated very explicitly, revealing how molecular-orbital theory can be used to provide "back-of-the-envelope" approximations to the reactivity indicators of conceptual DFT.

authors

  • Ayers, Paul
  • Morell, Christophe
  • De Proft, Frank
  • Geerlings, Paul

publication date

  • October 5, 2007