Quantitative analysis of charge transfer plasmons in silver nanocluster dimers using semiempirical methods

Plasmonic metal nanoclusters are widely used in chemistry, nanotechnology, and biomedicine. In metal nanocluster dimers, coupling of the plasmons leads to the emergence of two distinct types of modes: (1) bonding dipole plasmons (BDP), which occurs when charge oscillates synchronously within each nanocluster, and (2) charge transfer plasmons (CTP), which occurs when charge oscillates between two conductively linked nanoclusters. Although TDDFT-based modeling has uncovered some trends in these modes, it is computationally expensive for large dimers, and quantitative analysis is challenging. Here, we demonstrate that the semiempirical quantum mechanical method INDO/CIS enables us to quantify the CTP character of each excited state efficiently. In end-to-end Ag nanowire dimers, the longitudinal states have CTP character that decreases with increasing gap distance and nanowire length. In side-by-side dimers, the transverse states have CTP character and generally larger than in the end-to-end dimers, particularly for the longer nanowires. In side-by-side dimers where one nanowire is shifted along the length of the other, the CTP character of the longitudinal states peaks when the dimer is shifted by two Ag-Ag bond lengths, while the transverse states show decreasing CTP character as displacement increases. In the larger Ag₃₁⁺ nanorod dimers, CTP character follow a similar distance dependence to that seen in the small nanowire but have smaller overall CTP character than the nanowires. Our study demonstrates that INDO/CIS is capable of modeling metal nanocluster dimers at a low computational cost, making it possible to study larger dimers that are difficult to analyze using TDDFT.