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Title: Guided ion beam and theoretical studies of the bond energy of SmS +

Abstract

Previous work has shown that atomic samarium cations react with carbonyl sulfide to form SmS+ + CO in an exothermic and barrierless process. To characterize this reaction further, the bond energy of SmS+ is determined in the present study using guided ion beam tandem mass spectrometry. Reactions of SmS+ with Xe, CO, and O2 are examined. Results for collision-induced dissociation processes with all three molecules along with the endothermicity of the SmS+ + CO → Sm+ + COS exchange reaction are combined to yield D0(Sm+–S) = 3.37 ± 0.20 eV. The CO and O2 reactions also yield a SmSO+ product, with measured endothermicities that indicate D0(SSm+–O) = 3.73 ± 0.16 eV and D0(OSm+–S) = 1.38 ± 0.27 eV. The SmS+ bond energy is compared with theoretical values characterized at several levels of theory, including CCSD(T) complete basis set extrapolations using all-electron basis sets. Multireference configuration interaction calculations with explicit spin-orbit calculations along with composite thermochemistry using the Feller-Peterson-Dixon method and all-electron basis sets were also explored for SmS+, and for comparison, SmO, SmO+, and EuO

Authors:
ORCiD logo [1];  [1]; ORCiD logo [2]
  1. Univ. of Utah, Salt Lake City, UT (United States)
  2. Washington State Univ., Pullman, WA (United States)
Publication Date:
Research Org.:
Washington State Univ., Pullman, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1512934
Alternate Identifier(s):
OSTI ID: 1411286
Grant/Contract Number:  
SC0008501; FG02-12ER16329
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 147; Journal Issue: 21; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Armentrout, P. B., Demireva, Maria, and Peterson, Kirk A. Guided ion beam and theoretical studies of the bond energy of SmS +. United States: N. p., 2017. Web. doi:10.1063/1.5009916.
Armentrout, P. B., Demireva, Maria, & Peterson, Kirk A. Guided ion beam and theoretical studies of the bond energy of SmS +. United States. doi:10.1063/1.5009916.
Armentrout, P. B., Demireva, Maria, and Peterson, Kirk A. Tue . "Guided ion beam and theoretical studies of the bond energy of SmS +". United States. doi:10.1063/1.5009916. https://www.osti.gov/servlets/purl/1512934.
@article{osti_1512934,
title = {Guided ion beam and theoretical studies of the bond energy of SmS +},
author = {Armentrout, P. B. and Demireva, Maria and Peterson, Kirk A.},
abstractNote = {Previous work has shown that atomic samarium cations react with carbonyl sulfide to form SmS+ + CO in an exothermic and barrierless process. To characterize this reaction further, the bond energy of SmS+ is determined in the present study using guided ion beam tandem mass spectrometry. Reactions of SmS+ with Xe, CO, and O2 are examined. Results for collision-induced dissociation processes with all three molecules along with the endothermicity of the SmS+ + CO → Sm+ + COS exchange reaction are combined to yield D0(Sm+–S) = 3.37 ± 0.20 eV. The CO and O2 reactions also yield a SmSO+ product, with measured endothermicities that indicate D0(SSm+–O) = 3.73 ± 0.16 eV and D0(OSm+–S) = 1.38 ± 0.27 eV. The SmS+ bond energy is compared with theoretical values characterized at several levels of theory, including CCSD(T) complete basis set extrapolations using all-electron basis sets. Multireference configuration interaction calculations with explicit spin-orbit calculations along with composite thermochemistry using the Feller-Peterson-Dixon method and all-electron basis sets were also explored for SmS+, and for comparison, SmO, SmO+, and EuO},
doi = {10.1063/1.5009916},
journal = {Journal of Chemical Physics},
number = 21,
volume = 147,
place = {United States},
year = {2017},
month = {12}
}

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Figures / Tables:

FIG.  2 FIG. 2: Product ion cross sections as a function of center-of-mass (bottom x-axis) and laboratory (top x-axis) frame kinetic energy for the SmS+ reaction with CO. Solid lines are obtained by convoluting Eq. (2) with the model parameters in Table I for reactions ( 1) and (9)–(11) with the reactantmore » kinetic energy distributions. Dashed lines correspond to the model cross sections with no convolution over reactant internal and kinetic energy distributions.« less

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