Understanding the Woodward–Hoffmann Rules by Using Changes in Electron Density Journal Articles uri icon

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abstract

  • AbstractThe 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