Reduction of Dimerization Tendency Due to the Decrease in Hybridization Index by Inclusion of 4s and 4p Semicore States as Valence States in Mo_n (n=2-18) Clusters: A First-Principles Study

Owing to the unique structural, electronic, and physico-chemical properties, molybdenum clusters are expected to play an important role in future nanotechnologies. However, their ground states are still under debate. In this study, the crystal structure analysis by particle swarm optimization (CALYPSO) approach is used for the global minimum search, which is followed by first-principles calculations, to detect an obvious dimerization tendency in Mo _n ( n = 2 - 18) clusters when the 4s and 4p semicore states are not regarded as the valence states. Further, the clusters with even number of atoms are usually magic clusters with high stability. However, after including the 4s and 4p electrons as valence electrons, the dimerization tendency exhibits a drastic reduction because the average hybridization indices H_ \rmsp , H_ \rmsd , and H_ \rmpd are reduced significantly. Overall, this work reports new ground states of Mo _n ( n = 11, 14, 15) clusters and proves that semicore states are essential for Mo _n