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Durham University

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Publication details for Prof. Jan R.R. Verlet

Rogers, Joshua P., Anstöter, Cate S. & Verlet, Jan R. R. (2018). Evidence of Electron Capture of an Outgoing Photoelectron Wave by a Nonvalence State in (C6F6)n–. The Journal of Physical Chemistry Letters 9: 2504-2509.

Author(s) from Durham


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.