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Microhydration of caesium metaborate: structural and thermochemical properties of CsBO2 + n H2O (n = 1–4) aggregates

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Abstract

The structures and thermodynamic properties of microhydrates of caesium metaborate (CsBO2) of nuclear safety interest are reported in this work. CsBO2 + n H2O (n = 1−4) molecular complexes were identified on the potential energy surface. The structures were optimized using the ωB97XD DFT method and the aug-cc-pVTZ basis set. Single-point energies were calculated at the CCSD(T)-F12a/awCVTZ and the ωB97XD/aug-cc-pVQZ levels of theory. The standard reaction enthalpies and the standard Gibbs free reaction energies were reported for all molecular complexes. The temperature dependence of ΔrG°(T) was evaluated for all studied structures over the temperature range 300–2000 K. Total hydration reactions were investigated. The results showed that the mono-hydrated form of CsBO2 exists only at temperatures lower than 720 K under standard conditions. The influence on the thermodynamic properties of the number of water molecules in the clusters was described, with successive dehydration from 720 to 480 K. In nuclear severe accident conditions, gaseous CsBO2 will remain unhydrated in the reactor coolant system.

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Acknowledgments

Computer time for the theoretical calculations was provided by the Centre de Ressources Informatiques (CRI) of the University of Lille and the Centre Régional Informatique et d’Applications Numériques de Normandie (CRIANN). We appreciated the support from the LABEX CaPPA (Chemical and Physical Properties of the Atmosphere), which is funded by the French National Research Agency (ANR) through the PIA (Programme d’Investissement d’Avenir) under contract “ANR-11-LABX-0005-01 and also the Regional Council “Nord-Pas de Calais” and the “European Funds for Regional Economic Development”.

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Authors and Affiliations

  1. PhysicoChimie des Processus de Combustion et de l’Atmosphère (PC2A) UMR CNRS 8522, University of Lille, 59000, Lille, France

    Dorra Khiri, Romain Vandeputte, Sonia Taamalli & Florent Louis

  2. Laboratoire cinétique chimique, combustion et réactivité (C3R), Laboratoire de Recherche Commun IRSN-CNRS-Lille, Cadarache, 13115, St Paul Lez Durance, France

    Dorra Khiri, Romain Vandeputte, Sonia Taamalli, Laurent Cantrel & Florent Louis

  3. PSN-RES, Institut de Radioprotection et de Sûreté Nucléaire (IRSN), Cadarache, 13115, St Paul Lez Durance, France

    Romain Vandeputte & Laurent Cantrel

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  1. Dorra Khiri
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Correspondence to Florent Louis.

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Khiri, D., Vandeputte, R., Taamalli, S. et al. Microhydration of caesium metaborate: structural and thermochemical properties of CsBO2 + n H2O (n = 1–4) aggregates. J Mol Model 25, 207 (2019). https://doi.org/10.1007/s00894-019-4094-4

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