From Energetics to Intracluster Chemistry: Valence Photoionization of Trifluoromethylsulfur Pentafluoride (CF₃SF₅) by...

Trifluoromethylsulfur pentafluoride (CF₃SF₅) was valence threshold photoionized in a double imaging photoelectron photoion coincidence spectrometer using vacuum ultraviolet synchrotron radiation. In the 12.5-16.4 eV photon energy range, CF₃⁺, SF₅⁺, and SF₃⁺ cations were observed in both room temperature (RT) and molecular beam (MB) experiments. Their fractional abundances exhibited differences beyond the sample temperature. Kinetic energy analysis of the fragment ions confirmed the difference in the dissociative photoionization mechanism. In the RT experiment, the CF₃⁺ kinetic energies were extrapolated to a 11.84 ± 0.15 eV threshold, which was used in an ion cycle to determine the enthalpy of formation of CF₃SF₅ as Δ_fH°_298K(CF₃SF₅) = -1593 ± 16 kJ mol^-1. We also updated the enthalpy of formation of the sulfur pentafluoride radical as Δ_fH°_298K(SF₅) = -854 ± 7 kJ mol^-1 and discuss the discrepancy between the CF₃ ionization energy based on the Active Thermochemical Tables and the value anchored to the CF ionization energy. A computed reaction enthalpy network optimization resulted in Δ_fH°_298K(CF₃SF₅) = -1608 ± 20 kJ mol^-1. Both values for Δ_fH°_298K(CF₃SF₅) agree with previous ab initio ones in contrast to the original, experimental determination. SF₃⁺ is formed by F-transfer processes both in the RT and MB experiments. Although the same peaks were observed in both experiments, the lower SF₃⁺ onset energy and the more slowly rising CF₃⁺ kinetic energy release in the MB experiment revealed clustering and intracluster F-transfer reactions upon ionization. The monomer and dimer cation potential energy surfaces were explored to rationalize the observations. In the dimer cation, the observer CF₃SF₅ catalyzes fluorine transfer and promotes CF₄ formation, which ultimately leads to the SF₃⁺ fragment ion.