Collisional alignment and molecular rotation control the chemi-ionization of individual conformers of hydroquinone with metastable neon

The relationship between the shape of a molecule and its chemical reactivity is a central tenet in chemistry. However, the influence of the molecular geometry on reactivity can be subtle and result from several opposing effects. Here, using a crossed-molecular-beam experiment in which individual rotational quantum states of specific conformers of a molecule are separated, we study the chemi-ionization reaction of hydroquinone with metastable neon atoms. We show that collision-induced alignment of the reaction partners caused by geometry-dependent long-range forces influences reaction pathways, which is, however, countered by molecular rotation. The present work provides insights into the conformation-specific stereodynamics of complex polyatomic systems and illustrates the capability of advanced molecule-control techniques to unravel these effects. Molecular geometry can influence chemical reactivity through several opposing effects. By selecting individual conformers of hydroquinone in the chemi-ionization reaction with metastable neon, it is now shown that reaction pathways can be governed by molecular alignment due to geometry-dependent forces that are, however, countered by molecular rotation.