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Durham University

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Publication details for Prof. Jan R.R. Verlet

Rogers, Joshua P., Anstöter, Cate Sara, Bull, James N, Curchod, Basile F. E. & Verlet, Jan R. R. (2019). Photoelectron Spectroscopy of the Hexafluorobenzene Cluster Anions: (C6F6)n (n = 1 – 5) and I(C6F6). The Journal of Physical Chemistry A 123(8): 1602-1612.

Author(s) from Durham

Abstract

Frequency-resolved (2D) photoelectron (PE) spectra of the anionic clusters (C6F6)n, for n = 1 – 5, and time-resolved PE spectra of I(C6F6) are presented using a newly built instrument and supported by electronic structure calculations. From the 2D PE spectra, the vertical detachment energy (VDE) of C6F6 was measured to be 1.60 ± 0.01 eV and the adiabatic detachment energy (ADE) ≤ 0.70 eV. The PE spectra also contain fingerprints of resonance dynamics over certain photon energy ranges, in agreement with the calculations. An action spectrum over the lowest resonance is also presented. The 2D spectra of (C6F6)n show that the cluster can be described as (C6F6)(C6F6)n-1. The VDE increases linearly (200 ± 20 meV n−1) due to the stabilising influence on the anion of the solvating (C6F6) molecules. For I(C6F6), action spectra of the absorption just below both detachment channels are presented. Time-resolved PE spectra of I(C6F6) excited at 3.10 eV and probed at 1.55 eV reveal a short-lived non-valence state of (C6F6) that coherently evolves into the valence ground state of the anion and induces vibrational motion along a specific buckling coordinate. Electronic structure calculations along the displacement of this mode show that at the extreme buckling angle, the probe can access an excited state of the anion that is bound at that geometry, but adiabatically unbound. Hence, slow electrons are emitted and show dynamics that probe predominantly the outer-turning point of the motion. A PE spectrum taken at t = 0 contains vibrational structure, assigned to a specific Raman and/or IR active mode of (C6F6).