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Microhydration of caesium compounds: Cs, CsOH, CsI and Cs2I2 complexes with one to three H2O molecules of nuclear safety interest

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Abstract

Structure and thermodynamic properties (standard enthalpies of formation and Gibbs free energies) of hydrated caesium species of nuclear safety interest, Cs, CsOH, CsI and its dimer Cs2I2, with one up to three water molecules, are calculated to assess their possible existence in severe accident occurring to a pressurized water reactor. The calculations were performed using the coupled cluster theory including single, double and non-iterative triple substitutions (CCSD(T)) in conjunction with the basis sets (ANO-RCC) developed for scalar relativistic calculations. The second-order spin-free Douglas-Kroll-Hess Hamiltonian was used to account for the scalar relativistic effects. Thermodynamic properties obtained by these correlated ab initio calculations (entropies and thermal capacities at constant pressure as a function of temperature) are used in nuclear accident simulations using ASTEC/SOPHAEROS software. Interaction energies, standard enthalpies and Gibbs free energies of successive water molecules addition determine the ordering of the complexes. CsOH forms the most hydrated stable complexes followed by CsI, Cs2I2, and Cs. CsOH still exists in steam atmosphere even at quite high temperature, up to around 1100 K.

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Acknowledgments

We appreciate the support from the Slovak Research and Development Agency under the contract No. APVV-0059-10 and from the Comenius University Grant GUK/38/2013. Part of this work was done under the Research & Development Operational Program funded by the ERDF: Amplification of the Centre of Excellence on Green Chemistry Methods and Processes (CEGreen-II 26240120025). MS thanks SARNET for the support of her stay in Cadarache. A part of this work was carried out using the HELIOS supercomputer system at Computational Simulation Centre of International Fusion Energy Research Centre (IFERC-CSC), Aomori, Japan, under the Broader Approach collaboration between Euratom and Japan. This work has also beneficiated of the HPC resources from GENCI-IDRIS (Grant 2013-project number x2013086731).

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Authors and Affiliations

  1. Department of Physical and Theoretical Chemistry, Faculty of Natural Sciences, Comenius University, Mlynská dolina, 84215, Bratislava, Slovakia

    Mária Sudolská & Ivan Černušák

  2. Institut de Radioprotection et de Sûreté Nucléaire (IRSN), PSN-RES/SAG, Centre de Cadarache, F-13115, Saint Paul les Durance, France

    Laurent Cantrel

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  1. Mária Sudolská
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Correspondence to Mária Sudolská.

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This paper belongs to Topical Collection 9th European Conference on Computational Chemistry (EuCo-CC9).

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Sudolská, M., Cantrel, L. & Černušák, I. Microhydration of caesium compounds: Cs, CsOH, CsI and Cs2I2 complexes with one to three H2O molecules of nuclear safety interest. J Mol Model 20, 2218 (2014). https://doi.org/10.1007/s00894-014-2218-4

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