Vibrationally Mediated Stabilization of Electrons in Nonpolar Matter.

We explore solvation of electrons in nonpolar matter, here represented by butadiene clusters. Isolated butadiene supports only the existence of transient anions (resonances). Two-dimensional electron energy loss spectroscopy shows that the resonances lead to an efficient vibrational excitation of butadiene, which can result into the almost complete loss of energy of the interacting electron. Cluster-beam experiments show that molecular clusters of butadiene form stable anions, however only at sizes of more than 9 molecular units. We have calculated the distribution of electron affinities of clusters using classical and path integral molecular dynamics simulations. There is almost a continuous transition from the resonant to the bound anions with an increase in cluster size. The comparison of the classical and quantum dynamics reveals that the electron binding is strongly supported by molecular vibrations, brought about by nuclear zero-point motion and thermal agitation. We also inspected the structure of the solvated electron, finding it well localized.