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"Core sliding" in metal nanoclusters drives the reconstruction of external structural units and provides an ideal platform for mapping their precise transformation mechanism and evolution pathway. However, observing the movement behavior of metal atoms in experiments is still challenging because of the uncertain stability of intermediates. In this work, a series of Au-Cd alloy nanoclusters with continuously assembled kernels (one icosahedral building block assembled with 0 to 3 tetrahedral units) were constructed. As the assembly continued, it eventually led to the Cd atom doping into the inner positions of the clusters. Importantly, the Cd doped into the interior of the cluster exhibits a different behavior than the surface or external Cd atoms (dispersion doping vs localized occupy), which provides experimental evidence of the sliding behavior in the nanocluster kernel. Furthermore, density functional theory (DFT) calculations reveal that this sliding behavior in the inner sites of nanoclusters is an energetically favorable process. In addition, these Au-Cd nanoclusters exhibit tunable optical properties with different assembly patterns in their kernels.
Tan et al. (Mon,) studied this question.