We
present a microscopic theory for the description of fluctuation-induced
excitation energy transfer in chromophore dimers to explain experimental
data on a perylene biscarboximide dyad with orthogonal transition
dipole moments. Our non-Condon extension of Förster theory
takes into account the fluctuations of excitonic couplings linear
and quadratic in the normal coordinates, treated microscopically by
quantum chemical/electrostatic calculations. The modulation of the
optical transition energies of the chromophores is inferred from optical
spectra of the isolated chromophores. The application of the theory
to the considered dyad reveals a two to three order of magnitude increase
in the rate constant by non-Condon effects. These effects are found
to be dominated by fluctuations linear in the normal coordinates and
provide a structure-based qualitative interpretation of the experimental
time constant for energy transfer as well as its dependence on temperature.
Technical polymers could be identified by means of their remarkably strong auto fluorescence. The time constants of this fluorescence proved to be characteristic for the individual polymers and can be economically determined by integrating procedures. The thus obtained unequivocal identification is presented for their sorting for recycling. Furthermore, polymeric materials were doped with fluorescent dyes allowing a fine-classification of special batches.
Long-range interactions between electronically excited molecules and molecules at the ground state were found for distances of much more than 100 nm, as indicated by the dependence of the fluorescence lifetime on the concentration of dyes in diluted solutions. In contrast to this experimental result, the fluorescence lifetimes of distant isolated molecules should be independent from the concentration according to basic theory for light emission, such as that reported by Forster and Strickler−Berg. As a consequence, the theory of such emission should be modified for real systems to include electromagnetic interactions with distant resonating structures. Consequences of these findings concern many subjects, such as imaging methods (FLIM) in biochemistry.
Technical polymers could be identified by means of their remarkably strong auto fluorescence. The mono-exponentially obtained time constants of fluorescence decay were applied for a rough assignment of the polymeric materials whereas bi-exponential analysis allowed a fine classification such as for special batches and for preceding contaminations. Chemically similar materials such as LDPE (low-density polyethylene), HDPE (high-density polyethylene) and UHDPE (ultrahigh-density polyethylene) could be as well identified as contaminations of mineral oil in PET (polyethylene terephthalate). Furthermore, the fluorescence spectra could be characterized by means of five Gaussian functions in the visible allowing a redundant assignment to the fluorescence lifetimes. Thus, efficient sorting of polymers was possible for high performance recycling.
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