Role of electronic localization and charge-vibrational coupling in resonant photoelectron spectra of polymers: Application to poly(para-phenylenevinylene)

A combination of x-ray absorption and resonant photoemission (RPE) spectroscopy has been used to study the electronic structure of the one-dimensional conjugated polymer poly(para-phenylenevinylene) in nonordered (as prepared) thin films. The dispersion of RPE features for the decay to localized and delocalized bands are qualitatively different. A theory for band dispersion of RPE in polymers is given, showing the important roles of electronic state localization and vibrational (phonon) excitations for the character of the dispersion.