Influence of Interchain Interactions on the Absorption and Luminescence of Conjugated Oligomers and Polymers: A Quantum-Chemical Characterization

Abstract

Correlated quantum-chemical calculations are used to investigate the influence of interchain interactions on the absorption and emission of π-conjugated chains. The results are discussed in relation to the utilization of conjugated materials as active elements in electro-optic devices; they provide guidelines on how to prevent a substantial decrease in luminescence yield in solid films. In high-symmetry cofacial configurations, interchain interactions lead to a blue shift of the lowest optical transition compared to that calculated for an isolated chain; the appearance of an additional red-shifted component is expected when positional disorder is considered. The absence of any significant oscillator strength in the transition between the ground state and the lowest excited state in highly symmetric complexes implies that the luminescence emission will be strongly quenched. This picture is, however, modified when one takes account of the relaxation processes which occur in the lowest excited state. The nature of the most stable photogenerated species and the role played by chemical impurities are also addressed.