Activation of prototypical bonds by actinide atoms is an important aspect of material activity, and the results can be used for the study of nuclear material storage. In this study, the activation of the P–H bonds of the PH3 molecule by U or Th to form uranium or thorium hydride phosphorus has been systematically explored using density functional theory. A detailed description of the reaction mechanism which includes the potential energy profiles and the properties of bond evolution is presented. There are two types of reaction channels, isomerization and dehydrogenation in U + PH3 and Th + PH3. The difference between the two reactions is the process of the first P–H bond dissociation. The evolution characteristics of the chemical bonds along reaction pathways is analyzed by using electron localization functions, quantum theory of atoms in molecules, Mayer bond orders and natural bond orbitals. The reaction rate constants are calculated at the variational transition state level, and rate-determining steps are predicted.
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