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Journal Article

Communication: Revised electron affinity of SF6 from kinetic data.


Troe,  J.
Emeritus Group of Spectroscopy and Photochemical Kinetics, MPI for Biophysical Chemistry, Max Planck Society;

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Troe, J., Miller, T. M., & Viggiano, A. A. (2012). Communication: Revised electron affinity of SF6 from kinetic data. The Journal of Chemical Physics, 136(12): 121102. doi:10.1063/1.3698170.

Cite as: https://hdl.handle.net/11858/00-001M-0000-000F-A0CD-D
Previously determined experimental data for thermal attachment of electrons to SF 6 and thermal detachment from SF 6 − over the range 590–670 K are reevaluated by a third-law analysis. Recent high precision calculations of SF 6 − harmonic frequences and anharmonicities (for several of the modes) lead to considerable changes in modeled vibrational partition functions which then have to be accommodated for by a smaller value of the derived adiabatic electron affinity EA of SF 6 . The previously estimated value of EA = 1.20 ( ± 0.05) eV in this way is reduced to a value of EA = 1.03 ( ± 0.05) eV. In addition, the bond dissociation energy E 0,dis for SF 6 − → SF 5 − + Fisre- duced to E 0,dis = 1.44 ( ± 0.05) eV. Finally, the consequences for modeled specific rate constants k det ( E,J ) of electron detachment from SF 6 − are discussed.