Second harmonic Rayleigh scattering optical activity of single Ag nanohelices in a liquid

Determining the chirality of molecules and nanoparticles often relies on circular dichroism and optical rotation: two chiral optical (chiroptical) effects in the linear optical regime. Although these linear effects are weak compared to nonlinear chiroptical effects, they have the advantage of being measured in isotropic liquids - free from the complications of anisotropy. Recently, a nonlinear effect: hyper-Rayleigh scattering optical activity (HRS OA) has been shown to reliably distinguish between the two chiral forms of Ag nanohelices, suspended in isotropic liquids. However, this first demonstration of HRS OA also opened new questions. For instance, at a fundamental level, it is not clear what the role of interactions between nanoparticles is. Moreover, the influence of the ultrafast pulse chirp is unknown. Here, we demonstrate HRS OA from well below two Ag nanohelices in the illumination volume, precluding any interactions. Additionally, we performed the first measurements of HRS depolarization ratios in this system and find a value of ≈1. We also show that HRS is highly robust against the chirp of the ultrafast pulses. An important reason for the strong (down to single nanohelix) sensitivity of our experiments is the large chiroptical interaction at the fundamental frequency; this point is illustrated with two sets of numerical simulations of the electromagnetic near-fields. Our results highlight HRS OA as a highly sensitive experimental method for characterization of chiral solutions/suspensions, in tiny illumination volumes.