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Bond energy of ThN+: A guided ion beam and quantum chemical investigation of the reactions of thorium cation with N2 and NO

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.5111534· OSTI ID:1557672
 [1];  [2];  [2];  [3]
  1. Univ. of Utah, Salt Lake City, UT (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  2. Univ. of Utah, Salt Lake City, UT (United States)
  3. Washington State Univ., Pullman, WA (United States)
+ Show Author Affiliations
Kinetic-energy dependent reactions of Th+ with N2 and NO are studied using a guided ion beam tandem mass spectrometer. The formation of ThO+ in the reaction of Th+ with NO is observed to be exothermic and barrierless with a reaction efficiency at low energies of 0.91 ± 0.18. Formation of ThN+ in the reactions of Th+ with N2 and NO is endothermic in both cases. The kinetic-energy dependent cross sections for formation of this product ion were evaluated to determine a 0 K bond dissociation energy (BDE) of D0(Th+–N) = 6.51 ± 0.08 eV, the first direct measurement of this BDE. Additionally, the reactions were explored by quantum chemical calculations, including a full Feller-Peterson-Dixon composite approach with correlation contributions up to CCSDTQ for ThN and ThN+, as well as more approximate CCSD(T) calculations where a semiempirical model was used to estimate spin-orbit energy contributions. As a result, the ThN+ BDE is found to be larger than those of the transition metal congeners, TiN+ along with estimated values for ZrN+ and HfN+, believed to be a result of the actinide contraction.
Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Univ. of Utah, Salt Lake City, UT (United States); Washington State Univ., Pullman, WA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
AC05-76RL01830; SC0008501; SC0012249
OSTI ID:
1557672
Alternate ID(s):
OSTI ID: 1543055
OSTI ID: 1658387
OSTI ID: 1593392
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 3 Vol. 151; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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Figures / Tables (13)

FIG. 1(p. 6)figure FIG. 1
FIG. 2(p. 6)figure FIG. 2
TABLE I(p. 7)table TABLE I
TABLE II(p. 7)table TABLE II
TABLE III(p. 8)table TABLE III
FIG. 3(p. 9)figure FIG. 3
TABLE IV(p. 9)table TABLE IV
TABLE V(p. 10)table TABLE V
FIG. 4(p. 11)figure FIG. 4
TABLE VI(p. 11)table TABLE VI
TABLE VII(p. 12)table TABLE VII
FIG. 5(p. 13)figure FIG. 5
TABLE VIII(p. 14)table TABLE VIII

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Actinide chemistry
bond activation
gas-phase ion chemistry
tandem mass spectrometry
thermodynamics