Vibronic structure of PTCDA stacks: the exciton–phonon-charge-transfer dimer

Abstract Perylenetetracarboxylic acid dianhydride (PTCDA) stacks face-to-face in crystals and multiple quantum wells (MQWs). Excitations of PTCDA stacks are mixed molecular (Frenkel) and charge-transfer (CT) states coupled to a molecular vibration. Eclipsed stacks and molecular conjugation imply strong Frenkel–CT mixing in absorption and electroabsorption, with k=0 at the top of the exciton band, and negligible mixing at k=π for emission from the bottom. The exciton–phonon-CT dimer developed for k=0 processes is a nonadiabatic approximation for narrow CT bands. Quantitative dimer spectra are obtained in the vibronic basis of displaced harmonic oscillators for excited PTCDA and radical ions. We present a joint analysis of absorption and emission in PTCDA stacks and MQWs using parameters from solution, molecular calculations, and related conjugated systems. Polarized single-crystal absorption decisively relates the entire 2–3 eV system to molecular π–π* transitions, while electroabsorption with field along the stack implicates adjacent ions in the stack. The simple structure and extensive PTCDA spectra make possible detailed modelling of mixed Frenkel–CT vibronics that were far less accessible in previous organic molecular crystals. Since the coupled mode is closely related to polyenes and conjugated polymers, PTCDA provides a bridge between molecular insulators and extended systems capable of charge transport.