Woodward-Hoffmann rules in density functional theory: initial hardness response.

Abstract

The Woodward-Hoffmann rules for pericyclic reactions, a fundamental set of reactivity rules in organic chemistry, are formulated in the language of conceptual density functional theory (DFT). DFT provides an elegant framework to introduce chemical concepts and principles in a quantitative manner, partly because it is formulated without explicit reference to a wave function, on whose symmetry properties the Woodward-Hoffmann [J. Am. Chem. Soc. 87, 395 (1965)] rules are based. We have studied the initial chemical hardness response using a model reaction profile for two prototypical pericyclic reactions, the Diels-Alder cycloaddition of 1,3-butadiene to ethylene and the addition of ethylene to ethylene, both in the singlet ground state and in the first triplet excited state. For the reaction that is thermally allowed but photochemically forbidden, the initial hardness response is positive along the singlet reaction profile. (By contrast, for the triplet reaction profile, a negative hardness response is observed.) For the photochemically allowed, thermally forbidden reaction, the behavior of the chemical hardness along the initial stages of the singlet and triplet reaction profiles is reversed. This constitutes a first step in showing that chemical concepts from DFT can be invoked to explain results that would otherwise require invoking the phase of the wave function.