Inducing Enantioselectivity in Radiative Charge-Transfer Rates through Chiral Quantum Electrodynamic Fluctuations

Chiral discrimination has long been an important yet challenging topic in chemistry and physics. In this work, we study how chiral light-matter interaction under weak coupling regime enhances enantioselectivity of chiral charge transfer (CT) rates. Based on the framework of macroscopic quantum electrodynamics and Marcus electron transfer theory, we predict that the degree of discrimination (S) of a single-molecule asymmetric radiative CT reaction can achieve -2.0 × 10-2 through the light-matter interactions between a silicon nanohelix and a helicene-based CT dye. Orientation dependence of S is systematically analyzed, showing the averaged S < -10-3 for an isotropically oriented molecule. We further demonstrate that different molecular positions influence the orientation dependence of S. The results demonstrate how chiral vacuum electromagnetic fields influence enantioselectivity of radiative CT rates, opening up a new route to achieve chiral discrimination in molecular CT.