Anion
photoelectron (PE) spectroscopy was used to characterize
several perfluorocarbon (PFC) species generated from pulsed-laser
ablation of graphite fluoride (GF) and compare them to PFCs introduced
into the gas phase and negatively charged by using a gentle photoemission
source. The PE spectra of C6F6
–, C7F8
–, and C5F8
– produced by ablation of GF are nearly
identical with the PE spectra of the anions of hexafluorobenzene,
perfluorotoluene, and perfluorocyclopentene, respectively,
generated by electron attachment to the neutral perfluorocarbon molecules.
This result suggests that laser ablation of GF, which is a hyperthermal
decomposition event, produces species larger than CF2 and
with stable molecular structures. In addition, anion PE spectra were
obtained for several larger PFC molecular anions, some of which have
been the subject of past computational studies. The electron affinities
of these species cannot be determined unambiguously from the broad
PE spectra, though a systematic approach to identifying the onset
of detachment signal was used to approximate the electron affinities.
The vertical detachment energy of perfluoroethylcyclohexene
was determined to be 2.98 ± 0.05 eV. The vertical detachment
energies of additional perfluorocarbon radical anions, including perfluoroheptene,
perfluoromethylcyclohexane, perfluoro-1,3-dimethylcyclohexane,
and perfluorodecalin, all exceed 3.495 eV. We also demonstrated that
photoemission from gadolinia (Gd2O3) using a
pulsed laser is an efficient and effective method of generating radical
anions of larger volatile molecules in the gas phase.