Calculating curly arrows from ab initio wavefunctions.

Abstract

Despite being at the heart of chemical thought, the curly arrow notation of reaction mechanisms has been treated with suspicion-the connection with rigorous molecular quantum mechanics being unclear. The connection requires a view of the wavefunction that goes beyond molecular orbitals and rests on the most fundamental property of electrons. The antisymmetry of electronic wavefunctions requires that an N-electron wavefunction repeat itself in 3N dimensions, thus exhibiting tiles. Inspection of wavefunction tiles permits insight into structure and mechanism. Here, we demonstrate that analysis of the wavefunction tile along a reaction coordinate reveals the electron movements depicted by the curly arrow notation for several reactions. The Diels-Alder reaction is revealed to involve the separation and counter propagation of electron spins. This unprecedented method of extracting the movements of electrons during a chemical reaction is a breakthrough in connecting traditional depictions of chemical mechanism with state-of-the-art quantum chemical calculations.