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Exciton delocalization in conjugated polymer systems is determined by polymer conformationsand packing. Since exciton delocalization determines the photoluminescent vibronicprogression, optical spectroscopy provides an indirect link to polymer multiscale structures.This perspective describes our current theoretical understanding of how exciton delocalizationin π-conjugated polymers determines their optical spectroscopy, and further showshow exciton delocalization is related to conformational and environmental disorder. If themultiscale structures in conjugated polymer systems are known, then using first-principlesmodeling of excitonic processes it is possible to predict a wide-range of spectroscopic observables.We propose a reverse-engineering protocol of using these experimental observablesin combination with theoretical and computational modeling to determine the multiscalepolymers structures, thus establishing quantitative structure-function predictions

Perspective: Optical spectroscopy in π-conjugated polymers and how it can be used to determine multiscale polymer structures