Time-dependent optical linewidth in fluctuating environments: Stochastic models

Abstract

Time-resolved optical lineshapes are calculated using a second-order inhomogeneous cumulant expansion. The calculation shows that in the inhomogeneous limit the optical spectra are determined solely by two-time correlation functions. Therefore, measurements of the Stokes-shift correlation function and the inhomogeneous linewidth cannot provide information about the heterogeneity lifetime for systems exhibiting dynamic heterogeneities. The theoretical results are illustrated using a stochastic model for the optical transition frequencies. The model rests on the assumption that the transition frequencies are coupled to the environmental relaxation of the system. The latter is chosen according to a free-energy landscape model for dynamically heterogeneous dynamics. The model calculations show that the available experimental data are fully compatible with a heterogeneity lifetime on the order of the primary relaxation time.