Hydrolysis Reaction Pathways of Thorium Oxide Nanoclusters

Lontchi, Eddy M.; Vasiliu, Monica; Backman-Flamerich, Ryan; Jackson, Virgil E.; Dixon, David A.

doi:10.1021/acs.jpca.5c00981

Hydrolysis Reaction Pathways of Thorium Oxide Nanoclusters

Journal Article · Thu Apr 24 04:00:00 EDT 2025 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.5c00981· OSTI ID:3004801

Lontchi, Eddy M. ^[1]; Vasiliu, Monica ^[1]; Backman-Flamerich, Ryan ^[1]; Jackson, Virgil E. ^[1]; ^[1]

The University of Alabama, Tuscaloosa, AL (United States)

Density functional theory benchmarked by correlated molecular orbital theory is used to develop a fundamental and predictive understanding of the interaction of thorium oxide nanoclusters with gas phase water to provide insight into nuclear-waste storage, production of thorium nuclear reactor fuels, and reprocessing of spent fuel. The structures of Th_nO_2n (n = 3 – 6) clusters and their interactions with water have been studied at the B3LYP, MP2, and CCSD(T) levels. Hydrolysis is initiated by the formation of Lewis acid-base adducts, with relative H₂O binding energies (physisorption) ranging from −15 kcal/mol to −22 kcal/mol. The initial H₂O physisorption energy is ca. −21 kcal/mol regardless of the cluster size and is consistent with the experimentally obtained initial adsorption energy on a thorium dioxide surface. The physisorption enthalpies for additional water molecules can be affected by the presence of terminal groups OH groups generated by proton transfer to a Th-O near the site of adsorption. The hydrolysis products (chemisorption) form either bridging or terminal hydroxides. More exothermic hydrolysis steps were predicted for the formation of terminal hydroxides as compared to the formation of bridging hydroxides. Here, the calculated transition state barriers for transfer of protons from bound water complexes to form the chemisorption products are very low. Overall, water readily reacts with thorium oxide clusters preferring hydroxide products over hydrated complexes. First and second order fits were predicted for the combined physisorption and chemisorption energies for the hydrolysis of thorium oxide clusters. Ionization energies and electron affinities were calculated as were HOMO-LUMO gaps to provide additional insights into the properties of the thorium oxide and hydroxide clusters.

View Accepted Manuscript (DOE)

Research Organization:: University of Alabama, Tuscaloosa, AL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: SC0018921

OSTI ID:: 3004801

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 18 Vol. 129; ISSN 1089-5639; ISSN 1520-5215

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (48)

Reactions of Thorium Oxide Clusters with Water: The Effects of Oxygen Content Wang, Bin; Ye, Shu; Zhang, Si‐Yuan ChemPhysChem, Vol. 24, Issue 7 https://doi.org/10.1002/cphc.202200701	journal	December 2022
Theoretical models incorporating electron correlation Pople, John A.; Binkley, J. Stephen; Seeger, Rolf International Journal of Quantum Chemistry, Vol. 10, Issue S10 https://doi.org/10.1002/qua.560100802	journal	January 1976
Thermodynamic Properties of Actinides and Actinide Compounds Konings, Rudy J. M.; Morss, Lester R.; Fuger, Jean The Chemistry of the Actinide and Transactinide Elements https://doi.org/10.1007/978-94-007-0211-0_19	book	January 2010
Quantum electrodynamical corrections to the fine structure of helium Douglas, Marvin; Kroll, Norman M. Annals of Physics, Vol. 82, Issue 1 https://doi.org/10.1016/0003-4916(74)90333-9	journal	January 1974
The oxidation of thorium, uranium, and plutonium Colmenares, C. A. Progress in Solid State Chemistry, Vol. 9 https://doi.org/10.1016/0079-6786(75)90016-3	journal	January 1975
A fifth-order perturbation comparison of electron correlation theories Raghavachari, Krishnan; Trucks, Gary W.; Pople, John A. Chemical Physics Letters, Vol. 157, Issue 6 https://doi.org/10.1016/S0009-2614(89)87395-6	journal	May 1989
Plutonium in groundwater at the 100K-Area of the U.S. DOE Hanford Site Dai, Minhan; Buesseler, Ken O.; Pike, Steven M. Journal of Contaminant Hydrology, Vol. 76, Issue 3-4 https://doi.org/10.1016/j.jconhyd.2004.08.004	journal	February 2005
A short history of waste management at the Hanford Site Gephart, Roy E. Physics and Chemistry of the Earth, Parts A/B/C, Vol. 35, Issue 6-8 https://doi.org/10.1016/j.pce.2010.03.032	journal	January 2010
Hydrolysis of Small Oxo/Hydroxo Molecules Containing High Oxidation State Actinides (Th, Pa, U, Np, Pu): A Computational Study Lontchi, Eddy M.; Vasiliu, Monica; Tatina, Lauren M. The Journal of Physical Chemistry A, Vol. 125, Issue 28 https://doi.org/10.1021/acs.jpca.1c04048	journal	July 2021
Hydrolysis Reactions of the High Oxidation State Dimers Th₂O₄, Pa₂O₅, U₂O₆, and Np₂O₆. A Computational Study Lontchi, Eddy M.; Vasiliu, Monica; Dixon, David A. The Journal of Physical Chemistry A, Vol. 127, Issue 32 https://doi.org/10.1021/acs.jpca.3c03455	journal	August 2023
Molecular and Dissociative Adsorption of Water on (TiO ₂ ) _n Clusters, n = 1–4 Chen, Mingyang; Straatsma, Tjerk P.; Dixon, David A. The Journal of Physical Chemistry A, Vol. 119, Issue 46 https://doi.org/10.1021/acs.jpca.5b07697	journal	November 2015
Structural and Electronic Property Study of (ZnO) _n , n ≤ 168: Transition from Zinc Oxide Molecular Clusters to Ultrasmall Nanoparticles Chen, Mingyang; Straatsma, T. P.; Fang, Zongtang The Journal of Physical Chemistry C, Vol. 120, Issue 36 https://doi.org/10.1021/acs.jpcc.6b06730	journal	September 2016
Structures and Stabilities of (CaO) _n Nanoclusters Chen, Mingyang; Thanthiriwatte, K. Sahan; Dixon, David A. The Journal of Physical Chemistry C, Vol. 121, Issue 41 https://doi.org/10.1021/acs.jpcc.7b09062	journal	October 2017
Machine-Learning Approach for the Development of Structure–Energy Relationships of ZnO Nanoparticles Chen, Mingyang; Dixon, David A. The Journal of Physical Chemistry C, Vol. 122, Issue 32 https://doi.org/10.1021/acs.jpcc.8b01667	journal	July 2018
Stability and Electronic Properties of Rocksalt (CdO) _n , (SrO) _n , and (BaO) _n Nanoparticles Chen, Mingyang; Vasiliu, Monica; Hu, Shuxian The Journal of Physical Chemistry C, Vol. 122, Issue 43 https://doi.org/10.1021/acs.jpcc.8b07184	journal	September 2018
Zn_xMg_60–xO₆₀ Nanoclusters with Tunable Near-Ultraviolet Energy Gaps Chen, Mingyang; Shen, Kangqi; Saranya, Govindarajan The Journal of Physical Chemistry C, Vol. 123, Issue 20 https://doi.org/10.1021/acs.jpcc.9b00314	journal	May 2019
Conceptual Density Functional Theory Geerlings, P.; De Proft, F.; Langenaeker, W. Chemical Reviews, Vol. 103, Issue 5 https://doi.org/10.1021/cr990029p	journal	May 2003
Tree Growth—Hybrid Genetic Algorithm for Predicting the Structure of Small (TiO ₂ ) _n , n = 2–13, Nanoclusters Chen, Mingyang; Dixon, David A. Journal of Chemical Theory and Computation, Vol. 9, Issue 7 https://doi.org/10.1021/ct400105c	journal	June 2013
Should We Consider Using Liquid Fluoride Thorium Reactors for Power Generation? Cooper, Nicolas; Minakata, Daisuke; Begovic, Miroslav Environmental Science & Technology, Vol. 45, Issue 15 https://doi.org/10.1021/es2021318	journal	August 2011
Thorium(IV) Molecular Clusters with a Hexanuclear Th Core Knope, Karah E.; Wilson, Richard E.; Vasiliu, Monica Inorganic Chemistry, Vol. 50, Issue 19 https://doi.org/10.1021/ic2014946	journal	October 2011
Relativistic Density Functional Study on Uranium(IV) and Thorium(IV) Oxide Clusters of Zonohedral Geometry Shamov, Grigory A. Inorganic Chemistry, Vol. 51, Issue 12 https://doi.org/10.1021/ic2026522	journal	June 2012
Computational Study of the Hydrolysis Reactions of the Ground and First Excited Triplet States of Small TiO ₂ Nanoclusters Wang, Tsang-Hsiu; Fang, Zongtang; Gist, Natalie W. The Journal of Physical Chemistry C, Vol. 115, Issue 19 https://doi.org/10.1021/jp111026x	journal	April 2011
Computational Study of the Hydrolysis Reactions of Small MO ₂ (M = Zr and Hf) Nanoclusters with Water Fang, Zongtang; Outlaw, Matthew D.; Smith, Kyle K. The Journal of Physical Chemistry C, Vol. 116, Issue 15 https://doi.org/10.1021/jp210867w	journal	April 2012
Structures and Stabilities of (MgO) _n Nanoclusters Chen, Mingyang; Felmy, Andrew R.; Dixon, David A. The Journal of Physical Chemistry A, Vol. 118, Issue 17 https://doi.org/10.1021/jp412820z	journal	April 2014
Relativistic Small-Core Pseudopotentials for Actinium, Thorium, and Protactinium Weigand, Anna; Cao, Xiaoyan; Hangele, Tim The Journal of Physical Chemistry A, Vol. 118, Issue 13 https://doi.org/10.1021/jp500215z	journal	March 2014
Molecular Structures and Energetics of the (TiO ₂ ) _n ( n = 1−4) Clusters and Their Anions Li, Shenggang; Dixon, David A. The Journal of Physical Chemistry A, Vol. 112, Issue 29 https://doi.org/10.1021/jp800170q	journal	July 2008
Actinide Dioxides in Water: Interactions at the Interface Alexandrov, Vitaly; Shvareva, Tatiana Y.; Hayun, Shmuel The Journal of Physical Chemistry Letters, Vol. 2, Issue 24 https://doi.org/10.1021/jz201458x	journal	November 2011
Modeling the formation of TiO₂ ultra-small nanoparticles Chen, Mingyang; Dixon, David A. Nanoscale, Vol. 9, Issue 21 https://doi.org/10.1039/C7NR01749A	journal	January 2017
Unraveling the structural stability and the electronic structure of ThO₂ clusters Aguirre, Néstor F.; Jung, Julie; Yang, Ping Physical Chemistry Chemical Physics, Vol. 22, Issue 33 https://doi.org/10.1039/D0CP00478B	journal	January 2020
Validation of Koopmans' theorem for density functional theory binding energies Pueyo Bellafont, Noèlia; Illas, Francesc; Bagus, Paul S. Physical Chemistry Chemical Physics, Vol. 17, Issue 6 https://doi.org/10.1039/c4cp05434b	journal	January 2015
Parallel Douglas–Kroll energy and gradients in NWChem: Estimating scalar relativistic effects using Douglas–Kroll contracted basis sets de Jong, W. A.; Harrison, R. J.; Dixon, D. A. The Journal of Chemical Physics, Vol. 114, Issue 1 https://doi.org/10.1063/1.1329891	journal	January 2001
The generalized Douglas–Kroll transformation Wolf, Alexander; Reiher, Markus; Hess, Bernd Artur The Journal of Chemical Physics, Vol. 117, Issue 20 https://doi.org/10.1063/1.1515314	journal	November 2002
On Koopmans’ theorem in density functional theory Tsuneda, Takao; Song, Jong-Won; Suzuki, Satoshi The Journal of Chemical Physics, Vol. 133, Issue 17 https://doi.org/10.1063/1.3491272	journal	November 2010
A full coupled‐cluster singles and doubles model: The inclusion of disconnected triples Purvis, George D.; Bartlett, Rodney J. The Journal of Chemical Physics, Vol. 76, Issue 4 https://doi.org/10.1063/1.443164	journal	February 1982
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen Dunning, Thom H. The Journal of Chemical Physics, Vol. 90, Issue 2 https://doi.org/10.1063/1.456153	journal	January 1989
Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions Kendall, Rick A.; Dunning, Thom H.; Harrison, Robert J. The Journal of Chemical Physics, Vol. 96, Issue 9 https://doi.org/10.1063/1.462569	journal	May 1992
Coupled‐cluster methods with noniterative triple excitations for restricted open‐shell Hartree–Fock and other general single determinant reference functions. Energies and analytical gradients Watts, John D.; Gauss, Jürgen; Bartlett, Rodney J. The Journal of Chemical Physics, Vol. 98, Issue 11 https://doi.org/10.1063/1.464480	journal	June 1993
Density‐functional thermochemistry. III. The role of exact exchange Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652 https://doi.org/10.1063/1.464913	journal	April 1993
Correlation consistent basis sets for actinides. I. The Th and U atoms Peterson, Kirk A. The Journal of Chemical Physics, Vol. 142, Issue 7 https://doi.org/10.1063/1.4907596	journal	February 2015
Correlation consistent basis sets for actinides. II. The atoms Ac and Np–Lr Feng, Rulin; Peterson, Kirk A. The Journal of Chemical Physics, Vol. 147, Issue 8 https://doi.org/10.1063/1.4994725	journal	August 2017
The Molpro quantum chemistry package Werner, Hans-Joachim; Knowles, Peter J.; Manby, Frederick R. The Journal of Chemical Physics, Vol. 152, Issue 14 https://doi.org/10.1063/5.0005081	journal	April 2020
Note on an Approximation Treatment for Many-Electron Systems Møller, Chr.; Plesset, M. S. Physical Review, Vol. 46, Issue 7 https://doi.org/10.1103/PhysRev.46.618	journal	October 1934
Revision of the Douglas-Kroll transformation Jansen, Georg; Hess, Bernd A. Physical Review A, Vol. 39, Issue 11 https://doi.org/10.1103/PhysRevA.39.6016	journal	June 1989
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density Lee, Chengteh; Yang, Weitao; Parr, Robert G. Physical Review B, Vol. 37, Issue 2 https://doi.org/10.1103/PhysRevB.37.785	journal	January 1988
Coupled-cluster theory in quantum chemistry Bartlett, Rodney J.; Musiał, Monika Reviews of Modern Physics, Vol. 79, Issue 1 https://doi.org/10.1103/RevModPhys.79.291	journal	February 2007
Density-Functional Theory of the Electronic Structure of Molecules Parr, Robert G.; Yang, Weitao Annual Review of Physical Chemistry, Vol. 46, Issue 1 https://doi.org/10.1146/annurev.pc.46.100195.003413	journal	October 1995
Thorium-Fueled Underground Power Plant Based on Molten Salt Technology Moir, Ralph W.; Teller, Edward Nuclear Technology, Vol. 151, Issue 3 https://doi.org/10.13182/NT05-A3655	journal	September 2005
Liquid Fluoride Thorium Reactors Hargraves, Robert; Moir, Ralph American Scientist, Vol. 98, Issue 4 https://doi.org/10.1511/2010.85.304	journal	January 2010

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