On the contribution of the exciton–photon interaction to the exciton absorption line shape in the spatially inhomogeneous wave model: Application to the a-singlet exciton of naphthalene

Abstract

The problem of determining the contribution of the exciton–photon coupling to the absorption line shape or width of an exciton is addressed. In this regard, both the spatially homogeneous (polariton) and inhomogeneous wave models are considered. For the latter model, the theory is complex although a line shape expression is derived for the case of high exciton velocity and low oscillator strength. The related problem of determining the conditions under which the strong exciton–photon coupling limit is attained is also discussed. It is in this limit that light attenuation is independent of the oscillator strength. The theory plus new experimental data on the a exciton of naphthalene argue for the inadequacy of the polariton model. On the other hand, reasonable agreement between the data and the spatially inhomogeneous wave theory developed here is obtained. Thus, it is possible to estimate that the exciton–photon coupling contribution to the a‐exciton linewidth is 0.26 cm⁻¹. This is the major portion of the 2 K linewidth of 0.3 cm⁻¹.