Revealing the evolving mixture of molecular aggregates during organic film formation using simulations of in situ absorbance.

In this work, we introduce a method for modeling the evolving absorbance spectrum of an organic molecule, pseudoisocyanine (PIC), measured during the process of molecular aggregation. Despite being historically considered a J-aggregate, we find that the absorbance spectrum of PIC cannot be adequately modeled using solely J-aggregates either during molecular aggregation or in the final dry film. The collection of absorbance spectra during solution-casting is particularly difficult since a distribution of aggregates with various sizes and structures can coexist. Here, spectra measured during film formation are fit to a weighted sum of simulated spectra of two aggregate species, revealing the combinations of Coulombic coupling values, Huang-Rhys parameters, and aggregate sizes that provide good fits to measured spectra. The peak intensity ratios and relative peak positions are highly sensitive to the aggregate structure, and fitting only these features enables the rapid comparison of aggregate combinations. We find that the spectra of PIC aggregates cannot be modeled using the Huang-Rhys factor of the PIC monomer, as is typically assumed, leading us to consider models that utilize independent Huang-Rhys factors for each aggregate species. This method of fitting only the key spectral features allows an experimental spectrum to be modeled within 1 h-2 h when using a single Huang-Rhys factor, making the simulation of a series of in situ measurements during aggregation computationally feasible.