Evidence of Electron Capture of an Outgoing Photoelectron Wave by a Nonvalence State in (C₆F₆)_n^-

Frequency-resolved photoelectron spectra are presented for (C₆F₆)_n^- with n = 1-5 that show that C₆F₆^- is solvated by neutral C₆F₆ molecules. Direct photodetachment channels of C₆F₆^- are observed for all n, leaving the neutral in the S₀ ground state or triplet states, T₁ and T₂. For n ≥ 2, an additional indirect electron loss channel is observed when the triplet-state channels open. This indirect emission appears to arise from the electron capture of the outgoing photoelectron s-wave by a neutral solvent molecule through an anion nonvalence state. The same process is not observed for the S₀ detachment channel because the outgoing electron wave is predominantly a p-wave. Our results show that anion nonvalence states can act as electron-accepting states in cluster environments and can be viewed as precursor states for diffuse states of liquid C₆F₆.