What Contributes to the Measured Chiral Optical Response of the Glutathione-Protected Au25 Nanocluster?

The water-solubleglutathione-protected [Au-25(GSH)(18)](-1) nanocluster was investigatedby integratingseveral methodologies such as molecular dynamics simulations, essentialdynamics analysis, and state-of-the-art time-dependent density functionaltheory calculations. Fundamental aspects such as conformational, weakinteractions and solvent effects, especially hydrogen-bonds, wereincluded and found to play a fundamental role in assessing the opticalresponse of this system. Our analysis demonstrated not only that theelectronic circular dichroism is extremely sensitive to the solventpresence but also that the solvent itself plays an active role inthe optical activity of such system, forming a chiral solvation shellaround the cluster. Our work demonstrates a successful strategy toinvestigate in detail chiral interfaces between metal nanoclustersand their environments, applicable, e.g., to chiral electronic interactionsbetween clusters and biomolecules.

Automated summary

The water-soluble glutathione-protected [Au-25(GSH)(18)](-1) nanocluster was investigated using molecular dynamics simulations, essential dynamics analysis, and time-dependent density functional theory calculations. Conformational changes, weak interactions, and solvent effects, particularly hydrogen bonds, were found to significantly influence the optical response of the system. The analysis demonstrated the sensitive nature of the electronic circular dichroism to the presence of solvent and the active role of the solvent in forming a chiral solvation shell around the cluster. This work presents a successful strategy for studying chiral interfaces between metal nanoclusters and their environments, with potential applications in chiral electronic interactions with biomolecules.