Angle-Resolved Photoemission of Solvated Electrons in Sodium-Doped Clusters

TL;DR

This study uses angle-resolved photoelectron spectroscopy and calculations to investigate the nature of solvated electrons in sodium-doped clusters, revealing surface localization and the influence of hydrogen bonding.

Contribution

It provides experimental and theoretical evidence that solvated electrons in these clusters are surface-bound, challenging the idea of internal solvation in small clusters.

Findings

Electrons are surface-bound in studied clusters.

Ionization energies decrease with increasing cluster size.

Hydrogen bonding influences ionization energy trends.

Abstract

Angle-resolved photoelectron spectroscopy of the unpaired electron in sodium-doped water, methanol, ammonia, and dimethyl ether clusters is presented. The experimental observations and the complementary calculations are consistent with surface electrons for the cluster size range studied. Evidence against internally solvated electrons is provided by the photoelectron angular distribution. The trends in the ionization energies seem mainly determined by the degree of hydrogen bonding in the solvent and the solvation of the ion core. The onset ionization energies of water and methanol clusters do not level off at small cluster sizes, but decrease slightly with increasing cluster size.