Thiolate-protected gold nanoclusters(RS-AuNCs)have emerged as an ideal research system for unveiling intrinsic structure–property correlations due to their atomically precise structural tunability.This study addresse...Thiolate-protected gold nanoclusters(RS-AuNCs)have emerged as an ideal research system for unveiling intrinsic structure–property correlations due to their atomically precise structural tunability.This study addresses the structural absence and configuration stability controversies of face-centered cubic(FCC)-configured RS-AuNCs in the large-size regime of 102–191 gold atoms by establishing an innovative theoretical analysis framework.Through density functional theory(DFT)calculations,we successfully predicted for the first time a twinned-FCC Au127(SR)48 structure with C_(2) symmetry(Au127-x),which exhibits a remarkably small energy difference of merely 0.03 eV compared to the lowest-energy Dh configuration(Au127-w).This discovery strongly confirms the thermodynamic feasibility of FCC configurations in the 102-144 atom range.By integrating the‘kernel-differentiated fusion’growth mechanism with the‘divideand-protected’assembly strategy,we systematically constructed three large-sized FCC cluster models:Au164(SR)60,Au_(182)(SR)_(66) and Au_(188)(SR)_(66).The calculated average formation energies(Eave)validate the exceptional structural stability of these clusters.Strikingly divergent evolution patterns in HOMO–LUMO gaps are observed between shell-structured and cubic FCC-type RS-AuNCs across varying sizes,unambiguously demonstrating configuration-governed electronic structure modulation.More crucially,UV-Vis absorption spectra unveil emergent metallic signatures in both Au_(182)(SR)_(66) and Au_(188)(SR)_(66) clusters,thereby fundamentally redefining the critical size threshold for incipient metallicity in FCC-type RS-AuNCs.Breaking through traditional theoretical frameworks centered on‘size-configuration preference’,this research first elucidates the potential stability of FCC-configured RS-AuNCs within controversial size ranges.It not only addresses the existing size gap in structural models of large RS-AuNCs but also establishes a novel configuration design paradigm based on a‘kernel-differentiated fusion’strategy.展开更多
基金the financial support from the National Natural Science Foundation of China(Grant No.22203053)the Natural Science Foundation of Hunan Province(Grant No.2023JJ40606)+1 种基金Y.P.was financially supported by the National Natural Science Foundation of China(Grant No.22373082)the science and technology innovation program of Hunan Province(2023RC1055).
文摘Thiolate-protected gold nanoclusters(RS-AuNCs)have emerged as an ideal research system for unveiling intrinsic structure–property correlations due to their atomically precise structural tunability.This study addresses the structural absence and configuration stability controversies of face-centered cubic(FCC)-configured RS-AuNCs in the large-size regime of 102–191 gold atoms by establishing an innovative theoretical analysis framework.Through density functional theory(DFT)calculations,we successfully predicted for the first time a twinned-FCC Au127(SR)48 structure with C_(2) symmetry(Au127-x),which exhibits a remarkably small energy difference of merely 0.03 eV compared to the lowest-energy Dh configuration(Au127-w).This discovery strongly confirms the thermodynamic feasibility of FCC configurations in the 102-144 atom range.By integrating the‘kernel-differentiated fusion’growth mechanism with the‘divideand-protected’assembly strategy,we systematically constructed three large-sized FCC cluster models:Au164(SR)60,Au_(182)(SR)_(66) and Au_(188)(SR)_(66).The calculated average formation energies(Eave)validate the exceptional structural stability of these clusters.Strikingly divergent evolution patterns in HOMO–LUMO gaps are observed between shell-structured and cubic FCC-type RS-AuNCs across varying sizes,unambiguously demonstrating configuration-governed electronic structure modulation.More crucially,UV-Vis absorption spectra unveil emergent metallic signatures in both Au_(182)(SR)_(66) and Au_(188)(SR)_(66) clusters,thereby fundamentally redefining the critical size threshold for incipient metallicity in FCC-type RS-AuNCs.Breaking through traditional theoretical frameworks centered on‘size-configuration preference’,this research first elucidates the potential stability of FCC-configured RS-AuNCs within controversial size ranges.It not only addresses the existing size gap in structural models of large RS-AuNCs but also establishes a novel configuration design paradigm based on a‘kernel-differentiated fusion’strategy.
