Are the triple surface plasmon resonances in Zn nanoparticles true?

Abstract

It has been experimentally and numerically confirmed that zinc (Zn) nanoparticles (NPs) dispersed in silica exhibit two optical extinction peaks around ∼250 nm (1st peak) and ∼1050 nm (2nd peak), both of which were ascribed to surface plasmon resonances (SPRs) in the broad sense, i.e., the dual SPRs. Recently, Kuiri and Majhi (KM) observed the 3rd peak around ∼900 nm by calculations, and proposed the triple SPRs for Zn NPs without any experimental confirmation. This paper claims that the 3rd peak has never been observed in any experiments nor in any calculations except given by KM. They justified the triple resonances from an approximated SPR criterion, ε1Zn(ω) + 2ε1SiO2(ω) = 0, which is not valid for non-idealized metals like Zn, because the imaginary part of the dielectric function ε2Zn(ω) is not negligible. Instead, a rigorous SPR criterion predicts the dual resonances only. From comparisons with ab initio band calculations, the 1st and 2nd extinction peak are ascribed to resonantly enhanced inter-band transitions (so-called electronic resonance) and intra-band transitions (SPR in the narrow sense), respectively. Since either of the peaks arises from the resonant enhancement due to the dielectric function, both the peaks are regarded as SPRs in the broad sense, i.e. the dual SPRs.