CHIRALITY DISTRIBUTIONS THROUGH LIFETIME RESOLUTION IN FLUORESCENCE-DETECTED CIRCULAR-DICHROISM AND CIRCULARLY POLARIZED LUMINESCENCE - A THEORETICAL TREATMENT

Theoretical treatments are presented for a new technique, lifetime-resolved fluorescence-detected circular dichroism (LRFDCD). Two different experimental approaches are considered, one based on resolution of the separate emission signals for left and right circularly polarized excitation and the other on resolution of the differential and total signals. Both approaches resolve the signals into the Kuhn dissymmetry factor for each fluorescence lifetime component, producing the ground-state lifetime-chirality distribution for the sample; such resolution of chirality for multicomponent systems is not possible in the static fluorescence-detected circular dichroism (FDCD) experiment. Similar treatments are also given for lifetime-resolved circularly polarized luminescence (LRCPL), which yields the excited-state lifetime-chirality distribution that is composed of the luminescence dissymmetry factor for each lifetime component, and the combined technique of lifetime-resolved circularly polarized excitation/circularly polarized emission (LRCPECPL), which yields the product of the Kuhn and luminescence dissymmetry factors for each lifetime component. Lifetime resolution in both the time and frequency domains is considered.