Chirality in fluorescence and energy transfer

Optical polarization features associated with the fundamental processes of molecular fluorescence and resonance energy transfer are in general studied with reference to plane polarizations. When any of the species involved is chiral, the associated emission processes may exhibit an element of circular polarization—a degree of optical helicity. Although usually a minor effect, some systems can exhibit a sizeable component of circularly polarized luminescence, whose helicity correlates with the enantiomeric form. In studies of multi-component systems, in which initial excitation of a donor species—followed by energy transfer—leads to emission from an acceptor molecule, the handedness of both donor and acceptor may influence output circularity. In systems with an achiral acceptor, a degree of fluorescence circularity may be influenced by the handedness of a chiral donor, but this should not be construed in terms of 'conveying' chirality. Chiral molecules may also play a passive role by inducing helicity in the fluorescence from achiral neighbours, and further tiers of complexity arise if the initial excitation is itself of circular polarization. In all such processes, symmetry principles play a major role in determining a sensitivity to molecular handedness, and their detailed consideration enables a range of new experimental procedures to be identified. Casting the fundamental theory in terms of formal photon-molecule couplings enables the quantum mechanisms involved in all such phenomena to be clearly resolved. The results provide fresh physical insights, and establish connections across a range of indirectly related chiroptical phenomena including induced circular dichroism.