A single polymer chain can be thought of as a covalently bound J-aggregate, where the microscopic transition-dipole moments line up to emit in phase. Packing polymer chains into a bulk film can result in the opposite effect, inducing H-type coupling between chains. Cofacial transition-dipole moments oscillate out of phase, canceling each other out, so that the lowest-energy excited state turns dark. H-aggregates of conjugated polymers can, in principle, be coaxed into emitting light by mixing purely electronic and vibronic transitions. However, it is challenging to characterize this electron-phonon coupling experimentally. In a bulk film, many different conformations exist with varying degrees of intrachain J-type and interchain H-type coupling strengths, giving rise to broad and featureless aggregate absorption and emission spectra. Even if single nanoparticles consisting of only a few single chains are grown in a controlled fashion, the luminescence spectra remain broad, owing to the underlying molecular dynamics and structural heterogeneity at room temperature. At cryogenic temperatures, emission from H-type aggregates should be suppressed because, in the absence of thermal energy, internal conversion drives the aggregate to the lowest-energy dark state. At the same time, electronic and vibronic transitions narrow substantially, facilitating the attribution of spectral signatures to distinct vibrational modes. We demonstrate how to distinguish signatures of interchain H-type aggregate species from those of intramolecular J-type coupling. Whereas all dominant vibronic modes revealed in the photoluminescence (PL) and surface-enhanced resonance Raman scattering spectra of a single chromophore within a single polymer chain are identified in the J-type aggregate luminescence spectra, they are not all present at once in the H-type spectra. Universal spectral features are found for the luminescence from strongly HJ-coupled chains, clearly resolving the vibrations responsible for the nonadiabatic excited-state molecular dynamics that enable light emission. We discuss the possible combinations of vibrational modes responsible for H-type aggregate PL and demonstrate that only one, mainly the lowest energy one, of the three dominant vibrational modes contributes to the 0-1 transition, whereas combinations of all three are found in the 0-2 transition. From this analysis, we can distinguish between energy shifts due to either J-type intrachain coupling or H-type interchain interactions, offering a means to directly discriminate between structural and energetic disorder.
Keywords: H-aggregates; Herzberg−Teller coupling; SERS; conjugated polymers; cryogenic spectroscopy; single-molecule spectroscopy.