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

Richard M Cox; Murat Citir; P B Armentrout; Samuel R Battey; Kirk A Peterson

doi:10.1063/1.4948812

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

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

Richard M Cox, Murat Citir, P B Armentrout, Samuel R Battey and Kirk A Peterson

The Journal of chemical physics, Vol.144(18), pp.184309-184309

05/14/2016

DOI: https://doi.org/10.1063/1.4948812

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https://hdl.handle.net/2376/112856

PMID: 27179486

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Abstract

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. Finally, 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.

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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
Creators: Richard M Cox - Department of Chemistry, University of Utah, Salt Lake City, Utah 84112-0850, USA
Murat Citir - Department of Chemistry, University of Utah, Salt Lake City, Utah 84112-0850, USA
P B Armentrout - Department of Chemistry, University of Utah, Salt Lake City, Utah 84112-0850, USA
Samuel R Battey - Department of Chemistry, Washington State University, Pullman, Washington 99164-4630, USA
Kirk A Peterson - Department of Chemistry, Washington State University, Pullman, Washington 99164-4630, USA
Publication Details: The Journal of chemical physics, Vol.144(18), pp.184309-184309
Academic Unit: Chemistry, Department of
Publisher: United States
Identifiers: 99900548137501842
Language: English
Resource Type: Journal article