The effect of solvation on electron capture revealed using anion two-dimensional photoelectron spectroscopy.

The reaction of low-energy electrons with neutral molecules to form anions plays an important role in chemistry, being involved in, for example, various biological and astrochemical processes. However, key aspects of electron-molecule interactions, such as the effect of incremental solvation on the initially excited electronic resonances, remain poorly understood. Here two-dimensional photoelectron spectroscopy of anionic anthracene and nitrogen-substituted derivatives-solvated by up to five water molecules-reveals that for an incoming electron, resonances red-shift with increasing hydration; but for the anion, the excitation energies of the resonances remain essentially the same. These complementary points of view show that the observed onset of enhanced anion formation for a specific cluster size is mediated by a bound excited state of the anion. Our findings suggest that polycyclic aromatic hydrocarbons may be more efficient at electron capture than previously predicted with important consequences for the ionization fraction in dense molecular clouds.