A parametrized reactive force field model for aluminum ReaxFF Al has been developed based on density functional theory ͑DFT͒ data. A comparison has been made between DFT and ReaxFF Al outputs to ascertain whether ReaxFF Al is properly parametrized and to check if the output of the latter has correlation with DFT results. Further checks include comparing the equations of state of condensed phases of Al as calculated from DFT and ReaxFF Al . There is a good match between the two results, again showing that ReaxFF Al is correctly parametrized as per the DFT input. Simulated annealing has been performed on aluminum clusters Al n using ReaxFF Al to find the stable isomers of the clusters. A plot of stability function versus cluster size shows the existence of highly stable clusters ͑magic clusters͒. Quantum mechanically these magic clusters arise due to the complete filling of the orbital shells. However, since force fields do not care about electrons but work on the assumption of validity of Born-Oppenheimer approximation, the magic clusters are therefore correlated with high structural symmetry. There is a rapid decline in surface energy contribution due to the triangulated nature of the surface atoms leading to higher coordination number. The bulk binding energy is computed to be 76.8 kcal/mol. This gives confidence in the suitability of ReaxFF for studying and understanding the underlying dynamics in aluminum clusters. In the quantification of the growth of cluster it is seen that as the size of the clusters increase there is preference for the coexistence of fcc/hcp orders at the expense of simple icosahedral ordering, although there is some contribution from distorted icosahedral ordering. It is found that even for aluminum clusters with 512 atoms distorted icosahedral ordering exists. For clusters with N Ն 256 atoms fcc ordering dominates, which implies that at this point we are already on the threshold of bulklike bonding.

We have parametrized a reactive force field for NaH, ReaxFF NaH , against a training set of ab initio derived data. To ascertain that ReaxFF NaH is properly parametrized, a comparison between ab initio heats of formation of small representative NaH clusters with ReaxFF NaH was done. The results and trend of ReaxFF NaH 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 NaH . There is a good match between the two results, showing that ReaxFF NaH is correctly parametrized by the ab initio training set. ReaxFF NaH has been used to study the dynamics of hydrogen desorption in NaH particles. We find that ReaxFF NaH 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.

Abstract. Parameterization of a reactive force field for NaH is done using ab initio derived data. The parameterized force field(ReaxFFjVai;f) is used to study the dynamics governing hydrogen desorption in NaH. During the abstraction process of surface molecular hydrogen charge transfer is found to be well described by the parameterized force field. To gain more insight into the mechanism governing structural transformation of NaH during thermal decomposition a heating run in a molecular dynamics simulation is done. The result shows that a clear signature of hydrogen desorption is the fall in potential energy surface during heating.

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