Structural predictions of three medium-sized thiolate-protected gold nanoclusters Au44(SR)30, Au56(SR)32, and Au60(SR)34

Abstract

The knowledge of structural evolution among thiolate-protected gold nanoclusters is not only helpful for understanding their structure–property relationship but also provides scientific evidence to rule-guided structure predictions of gold nanoclusters. In this paper, three new atomic structures of medium-sized thiolate-protected gold nanoclusters, i.e. Au₄₄(SR)₃₀, Au₅₆(SR)₃₂, and Au₆₀(SR)₃₄, are predicted based on the grand unified model and ring model. Two structural evolution rules, i.e., Au₄₄(SR)₂₈ + [Au₁₂(SR)₄] → Au₅₆(SR)₃₂ + [Au₁₂(SR)₄] → Au₆₈(SR)₃₆ and Au₄₄(SR)₃₀ + [Au₈(SR)₂] → Au₅₂(SR)₃₂ + [Au₈(SR)₂] → Au₆₀(SR)₃₄ + [Au₈(SR)₂] → Au₆₈(SR)₃₆, are explored. The generic growth patterns underlying both sequences of nanoclusters can be viewed as sequential addition of four and three highly stable tetrahedral Au₄ units on the cores, respectively. In addition, density functional theory calculations show that these three newly predicted gold nanoclusters have very close formation energies with their adjacent structures, large highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO–LUMO) gaps, and all-positive harmonic vibration frequencies, indicating their high stabilities.