The exciton model in molecular spectroscopy

Abstract

The molecular exciton model has received its most extensive development and application in the field of molecular crystals1'2. More recently, numerous applications to non-crystalline molecular composite systems have been made, including van der Waals and hydrogen-bonded dimers, trimers, and higher order aggregates. Another type of composite system has also been investigated, namely the composite molecule consisting of covalently bonded molecular units, with intrinsic individual unsaturated electronic systems so isolated by single bonds that but little or insignificant electronic overlap between units may occur. It is now well established that in molecular aggregates and in composite molecules, exciton effects may be observed if sufficiently strong electronic transitions exist in the component sub-units. The result of exciton splitting of excited states in the composite molecule may be the appearance of strong spectral shifts or splittings (which may be of the order of 2000 cm—1) of the absorption bands for the component molecules. At the same time, as a consequence of the exciton splitting of the excited state manifold, an enhancement of triplet state excitation may result. The purpose of this paper is to present a summary of the various type cases for molecular dimers, trimers and double and triple molecules in the description of the molecular exciton strong-coupling model. Then it will be shown by new experimental examples that, even in those cases where no significant exciton effect is observable in the singlet—singlet absorption spectrum for the composite molecule (intermediate and weak coupling cases), the enhancement of lowest triplet state excitation may still be conspicuous and significant. The ideas which are summarized in this paper have a curious history. Long ago, Kautsky and Merkel3 demonstrated experimentally that aggregation of dyes facilitated their action as photophysical sensitizers in photochemical reactions, at the same time diminishing their fluorescence efficiency. Kautsky attributed these easily demonstrated effects to enhancement of metastable state excitation in the aggregate dye. There is no doubt today that the metastable state he described is the lowest triplet state of the molecules studied. However, he did not distinguish between intrinsic and enhanced metastable (triplet) state excitation, so his interpretations were largely overlooked. Forster in l946 used the quasi-classical vector model to