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Free energies and mechanisms of water exchange around Uranyl from first principles molecular dynamics

Published online by Cambridge University Press:  07 February 2012

Raymond Atta-Fynn ,
Eric J. Bylaska  and
Wibe A. de Jong
Raymond Atta-Fynn
Affiliation:
Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, WA 99352
Eric J. Bylaska
Affiliation:
Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, WA 99352
Wibe A. de Jong
Affiliation:
Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, WA 99352
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Abstract

From density functional theory (DFT) based ab initio (Car-Parrinello) metadynamics, we compute the activation energies and mechanisms of water exchange between the first and second hydration shells of aqueous Uranyl (UO22+) using the primary hydration number of U as the reaction coordinate. The free energy and activation barrier of the water dissociation reaction [UO2(OH2)5]2+(aq) → [UO2(OH2)4]2+(aq) + H2O are 0.7 kcal and 4.7 kcal/mol respectively. The free energy is in good agreement with previous theoretical (-2.7 to +1.2 kcal/mol) and experimental (0.5 to 2.2 kcal/mol) data. The associative reaction [UO2(OH2)5]2+(aq) + H2O → [UO2(OH2)6]2+(aq) is short-lived with a free energy and activation barrier of +7.9 kcal/mol and +8.9 kca/mol respectively; it is therefore classified as associative-interchange. On the basis of the free energy differences and activation barriers, we predict that the dominant exchange mechanism between [UO2(OH2)5]2+(aq) and bulk water is dissociative.

Keywords

actinidewatersimulation
Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 1383: Symposium A – Material Challenges in Current and Future Nuclear Technologies , 2012 , mrsf11-1383-a07-06
Copyright
Copyright © Materials Research Society 2012

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