Probing quantum-mechanical level repulsion in disordered systems by means of time-resolved selectively-excited resonance fluorescence

We argue that the time-resolved spectrum of selectively-excited resonance fluorescence at low temperature provides a tool for probing the quantum-mechanical level repulsion in the Lifshits tail of the electronic density of states in a wide variety of disordered materials. The technique, based on detecting the fast growth of a fluorescence peak that is red-shifted relative to the excitation frequency, is demonstrated explicitly by simulations on linear Frenkel exciton chains.Comment: 4 pages, 4 figures, to appear in Phys. Rev. Let

Low-temperature dynamics of weakly localized Frenkel excitons in disordered linar chains

We calculate the temperature dependence of the fluorescence Stokes shift and the fluorescence decay time in linear Frenkel exciton systems resulting from the thermal redistribution of exciton population over the band states. The following factors, relevant to common experimental conditions, are accounted for in our kinetic model: (weak) localization of the exciton states by static disorder, coupling of the localized excitons to vibrations in the host medium, a possible non-equilibrium of the subsystem of localized Frenkel excitons on the time scale of the emission process, and different excitation conditions (resonant or non resonant). A Pauli master equation, with microscopically calculated transition rates, is used to describe the redistribution of the exciton population over the manifold of localized exciton states. We find a counterintuitive non-monotonic temperature dependence of the Stokes shift. In addition, we show that depending on experimental conditions, the observed fluorescence decay time may be determined by vibration-induced intra-band relaxation, rather than radiative relaxation to the ground state. The model considered has relevance to a wide variety of materials, such as linear molecular aggregates, conjugated polymers, and polysilanes.Comment: 15 pages, 8 figure

Localization properties of one-dimensional Frenkel excitons: Gaussian versus Lorentzian diagonal disorder

We compare localization properties of one-dimensional Frenkel excitons with Gaussian and Lorentzian uncorrelated diagonal disorder. We focus on the states of the Lifshits tail, which dominate the optical response and low-temperature energy transport in molecular J-aggregates. The absence of exchange narrowing in chains with Lorentzian disorder is shown to manifest itself in the disorder scaling of the localization length distribution. Also, we show that the local exciton level structure of the Lifshits tail differs substantially for these two types of disorder: In addition to the singlets and doublets of localized states near the bare band edge, strongly resembling those found for Gaussian disorder, for Lorentzian disorder two other types of states are found in this energy region as well, namely multiplets of three or four states localized on the same chain segment and isolated states localized on short segments. Finally, below the Lifshits tail, Lorentzian disorder induces strongly localized exciton states, centered around low energy sites, with localization properties that strongly depend on energy. For Gaussian disorder with a magnitude that does not exceed the exciton bandwidth, the likelihood to find such very deep states is exponentially small.Comment: 9 two-column pages, 4 figures, to appear in Phys. Rev.

Nonlinear resonance reflection from and transmission through a dense glassy system built up of oriented linear Frenkel chains: two-level models

A theoretical study of the resonance optical response of assemblies of oriented short (as compared to an optical wavelength) linear Frenkel chains is carried out using a two-level model. We show that both transmittivity and reflectivity of the film may behave in a bistable fashion and analyze how the effects found depend on the film thickness and on the inhomogeneous width of the exciton optical transition.Comment: 26 pages, 9 figure