Photoelectron imaging spectroscopy of (CS2)n -, n>4, reveals a new state with an electron binding energy smaller than that of any of the corresponding CS2- and C2S4- states known to date. With support from ab initio calculations, two long-lived, metastable binding motifs with small electron binding energies are discussed for these clusters. The first is a solvent network permeating state, where the excess electron is delocalized over a number of linear CS2 molecules. The second is an excited 2B1 state of the core CS2- anion stabilized at a slightly bent geometry by the solvation interactions. Based on the observed solvation-induced shifts in binding energy, the second motif is favored.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry