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Title: Bond energies of ThO+ and ThC+ : A guided ion beam and quantum chemical investigation of the reactions of thorium cation with O2 and CO

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4948812· OSTI ID:1471100
ORCiD logo [1];  [1];  [1];  [2]; ORCiD logo [2]
  1. Univ. of Utah, Salt Lake City, UT (United States). Dept. of Chemistry
  2. Washington State Univ., Pullman, WA (United States). Dept. of Chemistry
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Kinetic energy dependent reactions of Th+ with O2 and CO are studied using a guided ion beam tandem mass spectrometer. The formation of ThO+ in the reaction of Th+ with O2 is observed to be exothermic and barrierless with a reaction efficiency at low energies of k/kLGS = 1.21 ± 0.24 similar to the efficiency observed in ion cyclotron resonance experiments. Formation of ThO+ and ThC+ in the reaction of Th+ with CO is endothermic in both cases. The kinetic energy dependent cross sections for formation of these product ions were evaluated to determine 0 K bond dissociation energies (BDEs) of D0(Th+–O) = 8.57 ± 0.14 eV and D0(Th+–C) = 4.82 ± 0.29 eV. The present value of D0(Th+–O) is within experimental uncertainty of previously reported experimental values, whereas this is the first report of D0(Th+–C). Both BDEs are observed to be larger than those of their transition metal congeners, TiL+, ZrL+, and HfL+ (L = O and C), believed to be a result of lanthanide contraction. Additionally, the reactions were explored by quantum chemical calculations, including a full Feller-Peterson-Dixon composite approach with correlation contributions up to coupled-cluster singles and doubles with iterative triples and quadruples (CCSDTQ) for ThC, ThC+, ThO, and ThO+, as well as more approximate CCSD with perturbative (triples) [CCSD(T)] calculations where a semi-empirical model was used to estimate spin-orbit energy contributions. In conclusion, the ThO+ BDE is compared to other actinide (An) oxide cation BDEs and a simple model utilizing An+ promotion energies to the reactive state is used to estimate AnO+ and AnC+ BDEs. For AnO+, this model yields predictions that are typically within experimental uncertainty and performs better than density functional theory calculations presented previously.

Research Organization:
Univ. of Utah, Salt Lake City, UT (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012249; FG02-12ER16329; SC0008501
OSTI ID:
1471100
Alternate ID(s):
OSTI ID: 1253063
Journal Information:
Journal of Chemical Physics, Vol. 144, Issue 18; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 39 works
Citation information provided by
Web of Science

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