From Superatomic AU25(SR)_(18)- to Superatomic M@Au_(24)(SR)_(18)~q Core-Shell Clusters

摘要

Au_(25)(SH)_(18)- belongs to a new type of superatom that features an icosahedral Au_(13) core-shell structure and a protective layer of six RS(Au-SR)_2 motifs. This superatom has a magic number of 8 free electrons that fully fill the 1sand 1plevels ofthe electron-shell model. By applying this superatom concept tothe core-substitution chemistry of Au_(25)(SR)_(18)-, we first scanned the periodic table for the potential core atom Mby applying a simple rule derived from the 8-electron count and then optimized the selected candidates by density functional theory calculations tocreate many series ofM@Au_(24)(SR)_(18)~q core-shell nanoclusters. We found that 16 elements from groups 1, 2, and 10-14 of the periodic table can maintain both electronic and geometric structures of the original Au_(25)(SR)_(18)- magic cluster, indicating that the electron-counting rule based on the superatom concept ispowerful in predicting viable M@Au_(24)(SR)_(18)~q clusters. Our work opens up a promising area for experimental exploration.