Strengthening of the Coordination Shell by Counter Ions in Aqueous Th4+ Solutions

Atta-Fynn, Raymond; Bylaska, Eric J.; de Jong, Wibe A.

doi:10.1021/acs.jpca.6b09878

Title: Strengthening of the Coordination Shell by Counter Ions in Aqueous Th⁴⁺ Solutions

Journal Article · Thu Dec 01 00:00:00 EST 2016 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.6b09878· OSTI ID:1393600

Atta-Fynn, Raymond ^[1]; Bylaska, Eric J. ^[2];

^[3]

Univ. of Texas, Arlington, TX (United States). Dept. of Physics
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Computational Research Division

The presence of counterions in solutions containing highly charged metal cations can trigger processes such as ion-pair formation, hydrogen bond breakages and subsequent re-formation, and ligand exchanges. In this work, it is shown how halide (Cl ^-, Br ^-) and perchlorate (ClO₄^-) anions affect the strength of the primary solvent coordination shells around Th⁴⁺ using explicit-solvent and finite-temperature ab initio molecular dynamics modeling methods. The 9-fold solvent geometry was found to be the most stable hydration structure in each aqueous solution. Relative to the dilute aqueous solution, the presence of the counterions did not significantly alter the geometry of the primary hydration shell. However, the free energy analyses indicated that the 10-fold hydrated states were thermodynamically accessible in dilute and bromide aqueous solutions within 1 kcal/mol. Analysis of the results showed that the hydrogen bond lifetimes were longer and solvent exchange energy barriers were larger in solutions with counterions in comparison with the solution with no counterions. In conclusion, this implies that the presence of the counterions induces a strengthening of the Th⁴⁺ hydration shell.

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; AC05-00OR22725

OSTI ID:: 1393600

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 120, Issue 51; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 10 works

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