Electron-phonon coupling in oligo(para-phenylene)s is addressed in terms of the off-resonance Raman intensities of two distinct modes at 1220 and 1280 cm(-1). On the basis of Albrecht's theory, vibrational coupling and Raman intensities are calculated from first-principles quantum-chemical methods. A few-state model is used to evaluate the dependence of the mode intensities on oligomer length, planarity, and excitation wavelength. The link between electron delocalizationconjugation and Raman intensities is highlighted. Extending on prior studies, the present work focuses on providing an in-depth understanding of the origin of this correlation in addition to reproducing experimental findings. The model applied here allows us to interpret the results on a microscopic, quantum-mechanical basis and to relate the observed trends to the molecular orbital structure and nature of the excited states in this class of materials. We find quantitative agreement between the results of the calculations and those of measurements performed on oligo(para-phenylene)s of various chain lengths in the solid state and in solution.

We report on the morphological aspects of thin films prepared from a blue–green light‐emitting conjugated polymer, (methyl‐substituted ladder‐type poly(p‐phenylene, mLPPP)), blended with a solid‐state electrolyte composed either by a crown ether, dicyclohexano‐18‐crown‐6 (DCH18C6), or a high‐molecular‐weight poly(ethylene oxide) (HMWPEO), and a Li salt, lithium trifluoromethanesulfonate (LiCF3SO3, Li triflate (LiTf)), as they have been successfully applied in light‐emitting electrochemical cells (LECs). The surface morphologies of the blend layers were investigated using atomic force microscopy (AFM) in tapping mode, and the ion distribution was probed using X‐ray analysis by means of energy‐dispersive X‐ray spectrometry (EDXS) in the scanning electron microscope (SEM). We show that the two different phase‐separation processes, the complexation tendencies of the ionic species as well as the ionic transport numbers, have tremendous influence on the performances of the corresponding LECs, revealing either rectifying or symmetric optoelectronic characteristics in forward and reverse bias directions. This opens up new possibilities for tuning the optoelectronic properties of ion‐supported organic electronic devices.

In this work, we clarify the nature of a previously not precisely identified Fermi dyad in the frequency range around 1600 cm−1 in oligo( para-phenylenes). To this end, we deploy a novel method to calculate third order anharmonic coupling effects in molecules. This Fermi dyad is shown to yield important information on the structural properties of the investigated materials. The nature of all vibrations contributing to this quantum mechanical resonance phenomenon is explained on the basis of a detailed normal coordinate analysis. The anharmonic coupling is then closely investigated by applying our theoretical model. In particular, we discuss the intensity redistribution among the two components of the Fermi doublet as well as their energetic separation. Subsequently, we establish a relation between these features and the structural conformation of the molecules. We show, how oligomer length and planarity of these systems can be determined from experimental Raman spectra by extracting the positions and relative intensities of the two components of the Fermi doublet. Furthermore, this Fermi resonance is shown to be sensitive to chemical modification on the molecules such as deuteration or substitution. Finally, we extend our model to electronically excited states in this class of molecules, as well as to charged species.

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