Modeling the sorption dynamics of NaH using a reactive force field

We have parametrized a reactive force field for NaH, ReaxFF Na H , against a training set of ab initio derived data. To ascertain that ReaxFF Na H is properly parametrized, a comparison between ab initio heats of formation of small representative NaH clusters with ReaxFF Na H was done. The results and trend of ReaxFF Na H are found to be consistent with ab initio values. Further validation includes comparing the equations of state of condensed phases of Na and NaH as calculated from ab initio and ReaxFF Na H . There is a good match between the two results, showing that ReaxFF Na H is correctly parametrized by the ab initio training set. ReaxFF Na H has been used to study the dynamics of hydrogen desorption in NaH particles. We find that ReaxFF Na H properly describes the surface molecular hydrogen charge transfer during the abstraction process. Results on heat of desorption versus cluster size shows that there is a strong dependence on the heat of desorption on the particle size, which implies that nanostructuring enhances desorption process. To gain more insight into the structural transformations of NaH during thermal decomposition, we performed a heating run in a molecular dynamics simulation. These runs exhibit a series of drops in potential energy, associated with cluster fragmentation and desorption of molecular hydrogen. This is consistent with experimental evidence that NaH dissociates at its melting point into smaller fragments.