文摘
Density functional theory calculations were employed to investigate the nucleation and growth of small palladium clusters, up to Pd9, into a microcavity of the porous hyper-cross-linked polystyrene (HPS). The geometries and the electronic structures of the palladium clusters inside the HPS cavity, following the one-by-one atom addition, are affected by a counterbalance between the Pd鈥損henyl (Pd鈭捨? and Pd鈥揚d interactions. The analysis performed on energetics, cavity distortions, and cluster geometries indeed suggest that the cluster growth is dominated by the Pd鈭捨?interactions up to the formation of Pd4 aggregates, whereas the metal鈥搈etal interactions actually rule the growth of the larger clusters. The elasticity of the hyper-cross-linked polystyrene matrix also plays an important role in the cluster development processes.