Structural, energetic, and electronic properties of hydrogenated aluminum arsenide clusters

Abstract

The chemisorptions of hydrogen on aluminum arsenide clusters are studied with density functional theory (DFT). The on-top site is identified to be the most favorable chemisorptions site for hydrogen. And the Al-top site is the preferred one in the most cases for one hydrogen adsorption in (AlAs) n (n = 2, 5, 6, 8–15) clusters. Top on the neighboring Al and As atoms ground-state structures are found for two hydrogen adsorption on (AlAs) n except for (AlAs)2 cluster. The Al–As bond lengths decrease generally as the size of the cluster increases. And there is a slight increase in the mean Al–As bond lengths after H adsorption on the lowest-energy sites of the most AlAs clusters. In general, the binding energy of H and 2H are both found to decrease with an increase in the cluster size. And the result shows that large binding energies (BE) of a single hydrogen atom on small AlAs clusters and large highest occupied and lowest unoccupied molecular-orbital gaps for (AlAs)H and (AlAs)3H make these species behaving like magic clusters. Calculations on two hydrogen atoms on (AlAs) n clusters show large BE for (AlAs) n H2 with an odd number of n. The stability of these complexes is further studied from the fragmentation energies. (AlAs)7H2 and (AlAs)9H2 clusters are again suggested to be the stable clusters. On the other hand both the fragmentation energy and the binding energy for (AlAs)13H are close to the lowest values.