A complete characterization of the vibrational modes has been performed for neutral and anionic SF5OOX (X = H, F, and Cl) structures using density functional theory (DFT). We also calculated the adiabatic electron affinity, bond dissociation energy and heat of formation of neutral pentafluorosulfur peroxides species using several Gn methods, starting from geometries optimized with B3LYP, M06-2X and MP2 levels of theory. We found that the most accurate enthalpies (Table1) at 298 K for SF5OOH, SF5OOF, and SF5OOCl are obtained with the G4 level of theory with values of -255.90, -230.50 and -221.75 kcal mol-1, respectively. On the other hand, the unsigned errors (UEs) of these same compounds obtained with DFT (B3LYP) are 19.82, 18.47 and 20.86 kcal mol-1, respectively, which suggests that it overestimates the enthalpy values with respect to G4. As a consequence, the values from the G4 method are used as a reference. In addition, the S-F and S-Cl bonds present low energy of dissociation (on average 28.74 and 30.24 kcal.mol-1, respectively) compared to the S-H bond (87.16 kcal mol-1). This makes possible a dissociative electron attachment (DEA) of the S-X bond (with X = F, Cl) represented by the SF5OO-X + e- → SF5OO- + -X reaction, while a S-H dissociation presents a low probability. This work provides crucial energetic data to improve the chemical information and characterization of these structures previously obtained through experimental studies.

Ab initio computational thermochemistry of SF5OOX (X=H, F an Cl)

2019 Spring National Meeting

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