Control of intramolecular orbital alignment in the photodissociation of thiophenol: Conformational manipulation by chemical substitution

Abstract

(Graph Presented) Intramolecular orbital alignment can be controlled by conformational tuning of the initial wavepacket location on the two-dimensional potential-energy surfaces of thiophenol (see picture; CI = conical intersection). Chemical substitution induces conformational preference, leading to a dramatic change of the branching ratio between X̃ and à states of the phenylthiyl radical. © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.