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

Abstract

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 resultmore » 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.« less

Authors:
; ;  [1]; ; ;  [2]; ; ;  [3];  [4]
  1. Department of Chemistry, University of Utah, Salt Lake City, Utah 84112 (United States)
  2. Department of Chemistry, Emory University, Atlanta, Georgia 30322 (United States)
  3. Air Force Research Laboratory, Space Vehicles Directorate, Kirtland AFB, Albuquerque, New Mexico 87117 (United States)
  4. Department of Chemistry, University of North Florida, Jacksonville, Florida 32224 (United States)
Publication Date:
OSTI Identifier:
22415611
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 13; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; BINDING ENERGY; CHEMICAL BONDS; EV RANGE; EVALUATION; ION BEAMS; KINETIC ENERGY; MASS SPECTROSCOPY; MOLECULAR IONS; PHOTOELECTRON SPECTROSCOPY; PHOTOIONIZATION; REACTIVITY; SAMARIUM; SAMARIUM OXIDES; THERMOSPHERE

Citation Formats

Cox, Richard M, Kim, JungSoo, Armentrout, P. B., E-mail: armentrout@chem.utah.edu, E-mail: mheaven@emory.edu, E-mail: albert.viggiano@us.af.mil, Bartlett, Joshua, VanGundy, Robert A., Heaven, Michael C., E-mail: armentrout@chem.utah.edu, E-mail: mheaven@emory.edu, E-mail: albert.viggiano@us.af.mil, Ard, Shaun G., Shuman, Nicholas S., Viggiano, Albert A., E-mail: armentrout@chem.utah.edu, E-mail: mheaven@emory.edu, E-mail: albert.viggiano@us.af.mil, and Melko, Joshua J. Evaluation of the exothermicity of the chemi-ionization reaction Sm + O → SmO{sup +} + e{sup −}. United States: N. p., 2015. Web. doi:10.1063/1.4916396.
Cox, Richard M, Kim, JungSoo, Armentrout, P. B., E-mail: armentrout@chem.utah.edu, E-mail: mheaven@emory.edu, E-mail: albert.viggiano@us.af.mil, Bartlett, Joshua, VanGundy, Robert A., Heaven, Michael C., E-mail: armentrout@chem.utah.edu, E-mail: mheaven@emory.edu, E-mail: albert.viggiano@us.af.mil, Ard, Shaun G., Shuman, Nicholas S., Viggiano, Albert A., E-mail: armentrout@chem.utah.edu, E-mail: mheaven@emory.edu, E-mail: albert.viggiano@us.af.mil, & Melko, Joshua J. Evaluation of the exothermicity of the chemi-ionization reaction Sm + O → SmO{sup +} + e{sup −}. United States. doi:10.1063/1.4916396.
Cox, Richard M, Kim, JungSoo, Armentrout, P. B., E-mail: armentrout@chem.utah.edu, E-mail: mheaven@emory.edu, E-mail: albert.viggiano@us.af.mil, Bartlett, Joshua, VanGundy, Robert A., Heaven, Michael C., E-mail: armentrout@chem.utah.edu, E-mail: mheaven@emory.edu, E-mail: albert.viggiano@us.af.mil, Ard, Shaun G., Shuman, Nicholas S., Viggiano, Albert A., E-mail: armentrout@chem.utah.edu, E-mail: mheaven@emory.edu, E-mail: albert.viggiano@us.af.mil, and Melko, Joshua J. 2015. "Evaluation of the exothermicity of the chemi-ionization reaction Sm + O → SmO{sup +} + e{sup −}". United States. doi:10.1063/1.4916396.
@article{osti_22415611,
title = {Evaluation of the exothermicity of the chemi-ionization reaction Sm + O → SmO{sup +} + e{sup −}},
author = {Cox, Richard M and Kim, JungSoo and Armentrout, P. B., E-mail: armentrout@chem.utah.edu, E-mail: mheaven@emory.edu, E-mail: albert.viggiano@us.af.mil and Bartlett, Joshua and VanGundy, Robert A. and Heaven, Michael C., E-mail: armentrout@chem.utah.edu, E-mail: mheaven@emory.edu, E-mail: albert.viggiano@us.af.mil and Ard, Shaun G. and Shuman, Nicholas S. and Viggiano, Albert A., E-mail: armentrout@chem.utah.edu, E-mail: mheaven@emory.edu, E-mail: albert.viggiano@us.af.mil and Melko, Joshua J.},
abstractNote = {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.},
doi = {10.1063/1.4916396},
journal = {Journal of Chemical Physics},
number = 13,
volume = 142,
place = {United States},
year = 2015,
month = 4
}
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