Architectural Blueprint of FCC Gold Nanoclusters: Modular Assembly of Au₁₈₈(SR)₆₀ and Au₁₁₀(SR)₄₈ from Tetrahedral Au₄ and Octahedral Au₆ Geometric Modules

Employing the fundamental building blocks of face-centered cubic (FCC) crystals, tetrahedral Au₄, and octahedral Au₆ as innermost kernel structures, we predicted the geometric configurations of FCC-type Au₁₈₈(SR)₆₀ and Au₁₁₀(SR)₄₈ through core-shell growth patterns. Calculations of the average formation energy (<i>E</i>_ave) demonstrate the favorable structural stability of Au₁₈₈(SR)₆₀ and Au₁₁₀(SR)₄₈. The density of states (DOS) plot reveals discrete orbital energy levels in both clusters and molecule-like multipeak features in their absorption spectra, indicating their classification as excitons. Furthermore, in the core-shell FCC-type RS-AuNCs system, the variation of the HOMO-LUMO energy gap exhibits a markedly distinct behavior compared with cubic FCC-type RS-AuNCs, demonstrating a sharp decline analogous to the trend observed in large-sized <i>D</i>_<i>h</i> and <i>I</i>_<i>h</i> configuration systems. These phenomena highlight the pivotal role of cluster configurations in regulating their electronic structures, providing novel theoretical insights for understanding structure-property relationships in nanoclusters.