DFT study on size-dependent geometries, stabilities, and electronic properties of Au

The ab initio method based on density functional theory at the PW91PW91 level has been employed to systematically study the structures, stabilities, electronic, and magnetic properties of gold clusters with or without silicon/phosphorus doping. The optimized geometries show that the most stable isomers for AunSi2 and AunP2 (n = 1–8) clusters prefer a three-dimensional structure when n = 2 and n = 3 upwards, respectively, and they can be viewed as grown from the already observed Aun−1M2 (M = Si, P). The relative stabilities of calculated AunM2 (M = Si, P) clusters have been analyzed through the atomic average binding energy, fragmentation energy, second-order difference of energy, and HOMO-LUMO gap. A pronounced odd-even alternative phenomenon indicates that the clusters with even-numbered valence electrons possess a higher stability than their neighboring ones. For both systems, natural population analysis reveals that electronic properties of dopant atoms in the corresponding configuration are mainly related to s and p states. We also investigated magnetic effects of clusters as a function of cluster size, however, their oscillatory magnetic moments were found to vary inversely to the fragmentation energy, second-order difference of energy, and HOMO-LUMO gap