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Title: Mechanism and Energetics of the Hydrolysis of Th+ To Form Th(OD)3+ : Guided Ion Beam and Theoretical Studies of ThO+, ThO 2+, and OThOD + Reacting with D2O

Abstract

The kinetic energy dependences of the reactions of ThO+, ThO2+, and OThOD+ with D2O, ThO2+ with D2, and OThOD+ with Xe were studied using guided ion beam tandem mass spectrometry. Exothermic formation of OThOD+ is the dominant process observed in reactions of both ThO+ and ThO2+ with D2O. Minor products formed in endothermic reactions include ThO2+, DThO+, and ThO2D2+. OThOD+ is also formed in the reaction of ThO2+ with D2 but in an endothermic process. Collision-induced dissociation of OThOD+ with Xe leads to endothermic loss of the hydroxide ligand. OThOD+ reacts further with D2O to form the associative complex ThO3D3+, which is long-lived before dissociating back to the reactants. The OThOD+ D2O bond energy of the associative complex is measured to be 2.96 ± 0.05 eV by modeling the kinetic energy dependent cross section for association using a phase space theory (PST) model that rigorously conserves angular momentum. By comparison with theory, this bond energy identifies the ThO3D3+ species as the trihydroxide cation, Th(OD)3+. From the endothermic reactions and CID of OThOD+ with Xe, the OTh+-D, OTh+ -O, and OTh+ -OD bond dissociation energies are measured to be 2.33 ± 0.24, 4.66 ± 0.15, and 6.00 ± 0.17 eV, respectively.more » All four of these BDEs are experimentally determined for the first time and agree reasonably well with values calculated at the B3LYP, B3PW91, and PBE0 levels of theory with cc-pVQZ basis sets. Complete potential energy surfaces for all reactions were calculated at the B3LYP/cc-pVTZ level and elucidate the mechanisms for all processes observed.« less

Authors:
 [1]; ORCiD logo [1]
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  1. Univ. of Utah, Salt Lake City, UT (United States)
Publication Date:
Research Org.:
Univ. of Utah, Salt Lake City, UT (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1593385
Grant/Contract Number:  
SC0012249
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 123; Journal Issue: 28; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Kafle, Arjun, and Armentrout, P. B. Mechanism and Energetics of the Hydrolysis of Th+ To Form Th(OD)3+ : Guided Ion Beam and Theoretical Studies of ThO+, ThO 2+, and OThOD + Reacting with D2O. United States: N. p., 2019. Web. doi:10.1021/acs.jpca.9b03938.
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Kafle, Arjun, & Armentrout, P. B. Mechanism and Energetics of the Hydrolysis of Th+ To Form Th(OD)3+ : Guided Ion Beam and Theoretical Studies of ThO+, ThO 2+, and OThOD + Reacting with D2O. United States. https://doi.org/10.1021/acs.jpca.9b03938
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Kafle, Arjun, and Armentrout, P. B. Tue . "Mechanism and Energetics of the Hydrolysis of Th+ To Form Th(OD)3+ : Guided Ion Beam and Theoretical Studies of ThO+, ThO 2+, and OThOD + Reacting with D2O". United States. https://doi.org/10.1021/acs.jpca.9b03938. https://www.osti.gov/servlets/purl/1593385.
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@article{osti_1593385,
title = {Mechanism and Energetics of the Hydrolysis of Th+ To Form Th(OD)3+ : Guided Ion Beam and Theoretical Studies of ThO+, ThO 2+, and OThOD + Reacting with D2O},
author = {Kafle, Arjun and Armentrout, P. B.},
abstractNote = {The kinetic energy dependences of the reactions of ThO+, ThO2+, and OThOD+ with D2O, ThO2+ with D2, and OThOD+ with Xe were studied using guided ion beam tandem mass spectrometry. Exothermic formation of OThOD+ is the dominant process observed in reactions of both ThO+ and ThO2+ with D2O. Minor products formed in endothermic reactions include ThO2+, DThO+, and ThO2D2+. OThOD+ is also formed in the reaction of ThO2+ with D2 but in an endothermic process. Collision-induced dissociation of OThOD+ with Xe leads to endothermic loss of the hydroxide ligand. OThOD+ reacts further with D2O to form the associative complex ThO3D3+, which is long-lived before dissociating back to the reactants. The OThOD+ D2O bond energy of the associative complex is measured to be 2.96 ± 0.05 eV by modeling the kinetic energy dependent cross section for association using a phase space theory (PST) model that rigorously conserves angular momentum. By comparison with theory, this bond energy identifies the ThO3D3+ species as the trihydroxide cation, Th(OD)3+. From the endothermic reactions and CID of OThOD+ with Xe, the OTh+-D, OTh+ -O, and OTh+ -OD bond dissociation energies are measured to be 2.33 ± 0.24, 4.66 ± 0.15, and 6.00 ± 0.17 eV, respectively. All four of these BDEs are experimentally determined for the first time and agree reasonably well with values calculated at the B3LYP, B3PW91, and PBE0 levels of theory with cc-pVQZ basis sets. Complete potential energy surfaces for all reactions were calculated at the B3LYP/cc-pVTZ level and elucidate the mechanisms for all processes observed.},
doi = {10.1021/acs.jpca.9b03938},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 28,
volume = 123,
place = {United States},
year = {Tue Jun 18 00:00:00 EDT 2019},
month = {Tue Jun 18 00:00:00 EDT 2019}
}
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