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Developing polarizable potential for molecular dynamics of Cm(III)-carbonate complexes in liquid water

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Abstract

In this work we have developed a polarizable potential to study Cm(III) forming complexes with carbonate anions in liquid water. The potential was developed by employing an extension of the procedure that we used to study the hydration of lanthanoids(III) and actinoids(III). Force field performances were benchmarked against DFT results obtained by both geometry optimization and Car-Parrinello molecular dynamics. With this polarizable potential, we run extended molecular dynamics simulations in liquid water from which we were able to identify structural and dynamical properties of such systems. In particular, water exchange dynamics were analyzed in detail. We obtained an average of three water molecules in the first shell of Cm(III) that show a relatively fast exchange dynamic (faster than for bare ions). Summarizing these results, we were able to draw an analogy to the results from the lanthanoid(III) series. In particular, it seems that Cm(III) behaves more like Nd(III) than Gd(III), as one would expect based on the recent hydration results and on f orbital occupancy.

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Acknowledgments

We thank ANR 2010 JCJC 080701 ACLASOLV (Actinoids and Lanthanoids Solvation) for grant support and Grand Equipement National de Calcul Intensif (GENCI) (grant x2013071870) for generous allocation of computing time. We thank Mrs. Elizabeth A. Kish for careful reading of the manuscript.

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Authors and Affiliations

  1. CNRS, UMR 8587, Evry Cedex, France

    Riccardo Spezia & Yannick Jeanvoine

  2. Laboratoire Analyse et Modélisation pour la Biologie et l’Environnement, Université d’Evry Val d’Essonne, Bd F.Mitterrand, 91025, Evry Cedex, France

    Riccardo Spezia & Yannick Jeanvoine

  3. Départment de Chimie, Ecole Normale Supérieure, 24, rue Lhomond, Paris, France

    Rodolphe Vuilleumier

  4. UMR 8640 CNRS-ENS-UPMC, UPMC Univ Paris 06, 4 Place Jussieu, 75005, Paris, France

    Rodolphe Vuilleumier

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  1. Riccardo Spezia
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Correspondence to Riccardo Spezia.

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Spezia, R., Jeanvoine, Y. & Vuilleumier, R. Developing polarizable potential for molecular dynamics of Cm(III)-carbonate complexes in liquid water. J Mol Model 20, 2398 (2014). https://doi.org/10.1007/s00894-014-2398-y

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