Isomerism effects in relaxation dynamics of Au24(SR)16 thiolate-protected gold nanoclusters

Understanding the excited state behavior of isomeric structures of thiolate-protected gold nanoclusters is still a challenging task. In this paper, based on grand unified model and ring model for describing thiolate-protected gold nanoclusters, we have predicted four isomers of Au-24(SR)(16) nanoclusters. Density functional theory calculations show that the total energy of one of the predicted isomers is 0.1 eV lower in energy than previously crystallized isomer. The nonradiative relaxation dynamics simulations of Au-24(SH)(16) isomers are performed to reveal the effects of structural isomerism on relaxation process of the lowest energy states, in which that most of the low-excited states consist of core states. In addition, crystallized isomer possesses the shorter e-h recombination time, whereas the most stable isomer has the longer recombination time, which may be attributed to the synergistic effect of nonadiabatic coupling and decoherence time. Our results could provide practical guidance to predict new gold nanoclusters for future experimental synthesis, and stimulate the exploration of atomic structures of same sized gold nanoclusters for photovoltaic and optoelectronic devices.

Automated summary

Understanding the behavior of isomeric structures of thiolate-protected gold nanoclusters in their excited state is challenging. This study predicts four isomers of Au-24(SR)(16) nanoclusters based on grand unified model and ring model. Calculations using density functional theory show that one of the predicted isomers has an energy 0.1 eV lower than the previously crystallized isomer. Nonradiative relaxation dynamics simulations reveal that most of the low-excited states consist of core states. The results have practical implications for predicting new gold nanoclusters for experimental synthesis and exploring atomic structures for photovoltaic and optoelectronic devices.