Guided ion beam and theoretical study of the reactions of Os + with H 2, D 2, and HD

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Publication Type Journal Article
School or College College of Science
Department Chemistry
Creator Armentrout, Peter B.
Other Author Hinton, Christopher S.; Citir, Murat
Title Guided ion beam and theoretical study of the reactions of Os + with H 2, D 2, and HD
Date 2011
Description Reactions of the third-row transition metal cation Os+ with H2, D2, and HD to form OsH+ (OsD+) were studied using a guided ion beam tandem mass spectrometer. A flow tube ion source produces Os+ in its 6D (6s15d6) electronic ground state level. Corresponding state-specific reaction cross sections are obtained. The kinetic energy dependences of the cross sections for the endothermic formation of OsH+ and OsD+ are analyzed to give a 0 K bond dissociation energy of D0(Os+?H) = 2.45 ? 0.10 eV. Quantum chemical calculations are performed here at several levels of theory, with B3LYP approaches generally overestimating the experimental bond energy whereas results obtained using BHLYP and CCSD(T), coupled-cluster with single, double, and perturbative triple excitations, levels show good agreement. Theory also provides the electronic structures of these species and the potential energy surfaces for reaction. Results from the reactions with HD provide insight into the reaction mechanism and indicate that Os+ reacts via a direct reaction. We also compare this third-row transition metal system with the first-row and second-row congeners, Fe+ and Ru+, and find that Os+ reacts more efficiently with dihydrogen, forming a stronger M+? H bond. These differences can be attributed to the lanthanide contraction and relativistic effects.
Type Text
Publisher American Institute of Physics (AIP)
Volume 135
Issue 23
First Page 234302
Last Page 234301
DOI 10.1063/1.3669425
Language eng
Bibliographic Citation Hinton, C. S., Citir, M., & Armentrout, P. B. (2011). Guided ion beam and theoretical study of the reactions of Os + with H 2, D 2, and HD. Journal of Chemical Physics, 135(23), 234302-1-234302-11.
Rights Management ©American Institute of Physics. The following article appeared in Hinton, C. S., Citir, M., & Armentrout, P. B., Journal of Chemical Physics, 135(23), 2011. and may be found at http://dx.doi.org/10.1063/1.3669425.
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Reference URL https://collections.lib.utah.edu/ark:/87278/s65d98x1
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