Surface Enhanced Circular Dichroism of Oriented Chiral Molecules by Plasmonic Nanostructures

TL;DR

This paper introduces a finite element method to analyze surface-enhanced circular dichroism in systems with nanostructures and oriented chiral molecules, revealing phase matching as key to boosting CD signals for ultrasensitive chiral detection.

Contribution

It demonstrates how phase matching of electromagnetic fields and gradients around nanostructures can significantly enhance CD signals, especially considering electric quadrupole contributions in oriented molecules.

Findings

Plasmon-induced CD is sensitive to molecular orientation.

Electric quadrupole transitions can significantly influence CD signals.

Phase matching can amplify CD signals by nearly two orders of magnitude.

Abstract

We present a rigorous finite element method to calculate circular dichroism (CD) in various systems consisting of nanostructures and oriented chiral molecules with electric quadrupole transitions. The interaction between oriented molecule materials, which are regarded as anisotropic chiral media, and metallic nanostructures has been investigated. Our results show that the plasmon-induced CD is sensitive to the orientations of the molecules. In many cases, the contribution of molecular electric quadrupole transitions to the total CD signal can play a key role. More interesting, we have demonstrated that both the quadrupole- and dipole-based CD signals can be improved greatly by matching the phases for the electromagnetic fields and their gradients at different regions around the nanostructures, which are occupied by the oriented chiral molecules. Different regions might produce CD of opposite sign. When integrating over regions with only one side of the proposed nanostructure, we find that the CD-peak may be nearly hundreds-fold over the case of integrating both sides. We believe that these findings would be helpful for realizing ultrasensitive probing of chiral information for oriented molecules by plasmon-based nanotechnology.