Surface functionalized spherical nanoparticles: an optical assessment of local chirality

Electromagnetic radiation propagating through any molecular system typically experiences a characteristic change in its polarization state as a result of light-matter interaction. Circularly polarized light is commonly absorbed or scattered to an extent that is sensitive to the incident circularity, when it traverses a medium whose constituents are chiral. This research assesses specific modifications to the properties of circularly polarized light that arise on passage through a system of surface-functionalized spherical nanoparticles, through the influence of chiral molecules on their surfaces. Non-functionalized nanospheres of atomic constitution are usually inherently achiral, but can exhibit local chirality associated with such surface-bound chromophores. The principal result of this investigation is the quantification of functionally conferred nanoparticle chirality, manifest through optical measurements such as circularly polarized emission. The relative position of chiral chromophores fixed to a nanoparticle sphere are first determined by means of spherical coverage co-ordinate analysis. The total electromagnetic field received by a spatially fixed, remote detector is then determined. It is shown that bound chromophores will accommodate both electric and magnetic dipole transition moments, whose scalar product represents the physical and mathematical origin of chiral properties identified in the detected signal. The analysis concludes with discussion of the magnitude of circular differential optical effects, and their potential significance for the characterization of surface-functionalized nanoparticles.