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

作者：Sudolska Maria^*; Cantrel Laurent; Cernusak Ivan

来源：Journal of Molecular Modeling, 2014, 20(4): 2218.

DOI：10.1007/s00894-014-2218-4

• Caesium compounds
• Interaction energies
• Microhydration
• Non-covalent interactions
• Severe nuclear accident
• Thermodynamic properties

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.

• 出版日期2014-4