Evidence of Electron Capture of an Outgoing Photoelectron Wave by a Nonvalence State in (C₆F₆)_<i>n</i>^–

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.