Effective conjugation and Raman intensities in oligo(para-phenylene)s: A microscopic view from first-principles calculations

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 1280cm−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 delocalization∕conjugation 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.