Electronic coupling and coherences in disordered polymers: Femtosecond 2D-photon echo correlation spectroscopy, signatures of an excitonic two-segmental site system: A theoretical study

Abstract

The two-dimensional (2D) temporal shape of the (degenerate) three-pulse photon-echo (3-PPE) polarization P(3)(t′,τ12,τ23=0) has been theoretically analyzed for a weakly interacting two-site system (TSS) in the presence of site inhomogeneous broadening. The TSS has been modeled in terms of two identical, energy-degenerate, excitonically coupled pairs of electronic states in the site-representation (i.e., two S0 and S1 states forming a 4-level system). The 2D time-domain signal S(t′,τ12,τ23=0) has been derived in a closed-form solution which allowed to formulate the analytical Fourier transform analog under sequential δ-pulse excitation. The resulting 2D PE signal in frequency–frequency space S(ωt′,ωτ12) is formed in the region of the resonant, optical carrier frequency by, generally, four peaks, arranged at the edges of a square with distances determined by the excitonic coupling. The two diagonal peaks are of one-exciton origin, while the two off-diagonal (cross) peaks involve two-exciton effects, too. The relative heights of the four peaks are in distinct relation with the mutual orientation of the site-localized transition dipoles, thus these 2D line shapes serving as a structural probe for resonantly interacting molecules. The shapes of the peaks reflect the ratio between homogeneous and inhomogeneous dephasings and can be used for structural studies of statically disordered systems of TSS. The semiclassical two-site model is intended to provide a preparatory platform for mimicking electronically coupled segmental pairs dispersed in energy and space along the strongly disordered main chain contour. The results of the model calculation are taken to discuss the potential and the limitations of 2D line shape echo-spectroscopy in the study of short-range coherences and electronic coupling in π-conjugated polymers.