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.; Caccamo, Alyssa C.; Gomez, Amber N.; Gibson, John K.; Dixon, David A.

doi:10.1021/acs.jpca.1c04048

Hydrolysis of Small Oxo/Hydroxo Molecules Containing High Oxidation State Actinides (Th, Pa, U, Np, Pu): A Computational Study

Journal Article · Fri Jul 09 00:00:00 EDT 2021 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.1c04048· OSTI ID:1840949

Lontchi, Eddy M. ^[1]; Vasiliu, Monica ^[1]; Tatina, Lauren M. ^[1]; Caccamo, Alyssa C. ^[1]; Gomez, Amber N. ^[1]; ^[2]; ^[1]

Univ. of Alabama, Tuscaloosa, AL (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

The energetics of hydrolysis reactions for high oxidation states of oxo/hydroxo monomeric actinide species (Th^IVO₂, Pa^IVO₂, U^IVO₂, Pa^VO₂(OH), U^VO₂(OH), U^VIO₃, Np^VIO₃, Np^VIIO₃(OH), and Pu^VIIO₃(OH)) were calculated at the CCSD(T) level. The first step is the formation of a Lewis acid/base adduct with H₂O (hydration), followed by a proton transfer to form a dihydroxide molecule (hydrolysis); this process is repeated until all oxo groups are hydrolyzed. The physisorption (hydration) for each H₂O addition was predicted to be exothermic, ca. -20 kcal/mol. The hydrolysis products are preferred energetically over the hydration products for the +IV and +V oxidation states. The compounds with An^VI are a turning point in terms of favoring hydration over hydrolysis. For An^VIIO₃(OH), hydration products are preferred, and only two waters can bind; the complete hydrolysis process is now endothermic, and the oxidation state for the An in An(OH)₇ is +VI with two OH groups each having one-half an electron. The natural bond order charges and the reaction energies provide insights into the nature of the hydrolysis/hydration processes. The actinide charges and bond ionicity generally decrease across the period. Here, the ionic character decreases as the oxidation state and coordination number increase so that covalency increases moving to the right in the actinide period.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

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

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1840949

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: 28 Vol. 125; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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