Biexciton dynamics in molecular aggregates provides a sensitive probe of the interplay between quantum coherence, band structure, and dissipation under strong excitation conditions. We present a theoretical framework for biexciton dynamics in molecular aggregates that explicitly treats populations and coherences across excitation manifolds within a reduced density-matrix formalism. By extending kinetic descriptions beyond the weak-coupling limit, the approach captures the influence of exciton delocalization and exciton-exciton annihilation while remaining computationally tractable within a Markovian description of environmental relaxation. Using this framework, we investigate how the spatial profile and momentum composition of the initial biexciton state govern fluorescence decay and transport. Incoherent initial conditions lead to strongly non-exponential relaxation and time-dependent diffusion driven by nonlinear population kinetics. In contrast, coherently prepared biexciton states exhibit pronounced early-time coherent transport, whose character depends sensitively on whether the initial state is prepared as a standing-wave or traveling-wave superposition of single-exciton modes. Despite nearly identical emission dynamics for J and H aggregates, biexciton transport properties differ markedly due to band structure-dependent interference effects. Our results demonstrate that biexciton dynamics remains strongly influenced by initial-state coherence and momentum composition. In addition to the initial-state preparation, the coherent-to-incoherent crossover and the diffusive spreading of the exciton density are sensitive to internal conversion processes such as exciton fusion and the decay to the first excited state. The present work establishes initial-state preparation as a key control parameter for many-exciton transport in excitonic systems and provides a general framework for interpreting nonlinear optical experiments beyond population-based descriptions.
Dutta et al. (Thu,) studied this question.