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Frequency-resolved photoelectron spectra are presented for (C 6 F 6 ) n  - with n = 1-5 that show that C 6 F 6  - is solvated by neutral C 6 F 6 molecules. Direct photodetachment channels of C 6 F 6  - are observed for all n, leaving the neutral in the S 0 ground state or triplet states, T 1 and T 2 . 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 S 0 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 C 6 F 6 .

Evidence of Electron Capture of an Outgoing Photoelectron Wave by a Nonvalence State in (C6F6)n–

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