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Title: The role of cations in uranyl nanocluster association: a molecular dynamics study

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI: https://doi.org/10.1039/c9cp05138d · OSTI ID:1767694
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [3]
  1. Univ. of Notre Dame, Notre Dame, IN (United States); OSTI
  2. Univ. of Minnesota, Minneapolis, MN (United States)
  3. Univ. of Notre Dame, Notre Dame, IN (United States)
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Actinyl ions can self-assemble in aqueous solution to form closed cage clusters ranging from 1.5 to 4.0 nm in diameter. The self-assembly, stability, and behavior of the nanoclusters depend on the nature of the aqueous environment, such as the pH and cations present. In this work, a classical force field for [(UO2)20(O2)30]20- (U20) peroxide nanoclusters in aqueous solution was developed from quantum-mechanical calculations. Using molecular dynamics simulations, the preferred binding sites of six cations (Li+, Na+, K+, Rb+, Cs+, and Ca2+) to the nanocluster were determined. Replica exchange molecular dynamics was used to equilibrate the structure and determine the equilibrium distribution of cations and water with respect to the nanocluster cage. In addition, the free energy barriers associated with cations entering the cluster were computed. Finally, the association of two cages was investigated by computing the free energy as a function of intercage distance. The free energy profiles reveal that the nanoclusters prefer to be associated when neutralized with divalent cations, but do not associate when neutralized with monovalent cations. Finally, this could explain the formation of tertiary structures observed experimentally.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Materials Science of Actinides (MSA); Univ. of Notre Dame, IN (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0001089
OSTI ID:
1767694
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 4 Vol. 22; ISSN 1463-9076
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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