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Title: Evaluation of the exothermicity of the chemi-ionization reaction Sm + O → SmO{sup +} + e{sup −}

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4916396· OSTI ID:22415611
; ; ; ; ; ;  [1]
  1. Department of Chemistry, University of North Florida, Jacksonville, Florida 32224 (United States)

The exothermicity of the chemi-ionization reaction Sm + O → SmO{sup +} + e{sup −} has been re-evaluated through the combination of several experimental methods. The thermal reactivity (300–650 K) of Sm{sup +} and SmO{sup +} with a range of species measured using a selected ion flow tube-mass spectrometer apparatus is reported and provides limits for the bond strength of SmO{sup +}, 5.661 eV ≤ D{sub 0}(Sm{sup +}-O) ≤ 6.500 eV. A more precise value is measured to be 5.72{sub 5} ± 0.07 eV, bracketed by the observed reactivity of Sm{sup +} and SmO{sup +} with several species using a guided ion beam tandem mass spectrometer (GIBMS). Combined with the established Sm ionization energy (IE), this value indicates an exothermicity of the title reaction of 0.08 ± 0.07 eV, ∼0.2 eV smaller than previous determinations. In addition, the ionization energy of SmO has been measured by resonantly enhanced two-photon ionization and pulsed-field ionization zero kinetic energy photoelectron spectroscopy to be 5.7427 ± 0.0006 eV, significantly higher than the literature value. Combined with literature bond energies of SmO, this value indicates an exothermicity of the title reaction of 0.14 ± 0.17 eV, independent from and in agreement with the GIBMS result presented here. The evaluated thermochemistry also suggests that D{sub 0}(SmO) = 5.83 ± 0.07 eV, consistent with but more precise than the literature values. Implications of these results for interpretation of chemical release experiments in the thermosphere are discussed.

OSTI ID:
22415611
Journal Information:
Journal of Chemical Physics, Vol. 142, Issue 13; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
Country of Publication:
United States
Language:
English