Forbes Kayn A, Bradshaw David S, Andrews David L
School of Chemistry, University of East Anglia, Norwich NR4 7TJ, United Kingdom.
J Chem Phys. 2019 Jul 21;151(3):034305. doi: 10.1063/1.5109844.
Electronically excited molecules frequently exhibit two distinctive decay mechanisms that rapidly generate optical emission: one is direct fluorescence and the other is energy transfer to a neighboring component. In the latter, the process leading to the ensuing "indirect" fluorescence is known as FRET, or fluorescence resonance energy transfer. For chiral molecules, both fluorescence and FRET exhibit discriminatory behavior with respect to optical and material handedness. While chiral effects such as circular dichroism are well known, as too is chiral discrimination for FRET in isolation, this article presents a study on a stepwise mechanism that involves both. Chirally sensitive processes follow excitation through the absorption of circularly polarized light and are manifest in either direct or indirect fluorescence. Following recent studies setting down the symmetry principles, this analysis provides a rigorous, quantum outlook that complements and expands on these works. Circumventing expressions that contain complicated tensorial components, our results are amenable for determining representative numerical values for the relative importance of the various coupling processes. We discover that circular dichroism exerts a major influence on both fluorescence and FRET, and resolving the engagement of chirality in each component reveals the distinct roles of absorption and emission by, and between, donor and acceptor pairs. It emerges that chiral discrimination in the FRET stage is not, as might have been expected, the main arbiter in the stepwise mechanism. In the concluding discussion on various concepts, attention is focused on the validity of helicity transfer in FRET.
