Photon transport in cylindrically-shaped disordered meso-macroporous materials.

We theoretically and experimentally investigate light diffusion in disordered meso-macroporous materials with a cylindrical shape. High Internal Phase Emulsion (HIPE)-based silica foam samples, exhibiting a polydisperse pore-size distribution centered around 19 µm to resemble certain biological tissues, are realized. To quantify the effect of a finite lateral size on measurable quantities, an analytical model for diffusion in finite cylinders is developed and validated by Monte Carlo random walk simulations. Steady-state and time-resolved transmission experiments are performed and the transport parameters (transport mean free path and material absorption length) are successfully retrieved from fits of the experimental curves with the proposed model. This study reveals that scattering losses on the lateral sides of the samples are responsible for a lowering of the transmission signal and a shortening of the photon lifetime, similar in experimental observables to the effect of material absorption. The recognition of this geometrical effect is essential since its wrong attribution to material absorption could be detrimental in various applications, such as biological tissue diagnosis or conversion efficiency in dye-sensitized solar cells.

Single molecule probing of dynamics in supercooled polymers.

Fluorescence experiments with single BODIPY molecules embedded in a poly(methyl acrylate) matrix have been performed at various temperatures in the supercooled regime. By using pulsed excitation, fluorescence lifetime and linear dichroism time trajectories were accessible at the same time. Both observables have been analyzed without data binning. While the linear dichroism solely reflects single particle dynamics, the fluorescence lifetime observable depends on the molecular environment, so that the dynamics from the polymer host surrounding a chromophore contributes to this quantity. We observe that the lifetime correlation decays slightly faster than polarization correlation, indicating the occurrence of large angular reorientations. Additionally, dichroism time trajectories have been adducted to reveal directly the geometry of rotational dynamics. We identify small but also significantly larger rotational jumps being responsible for the overall molecular reorientation.

Probe molecules in polymer melts near the glass transition: A molecular dynamics study of chain length effects.

Molecular dynamics simulations of a dense melt of short bead-spring polymer chains containing N=5, 10, or 25 effective monomers are presented and analyzed. Parts of our simulations include also a single dumbbell (N=2) of the same type, which is interpreted to represent a coarse-grained model for a fluorescent probe molecule as used in corresponding experiments. We obtain the mean-square displacements of monomers and chains center of mass, and intermediate incoherent scattering functions of both monomers in the chains and particles in the dumbbells as function of time for a broad regime of temperatures above the critical temperature T(c) of mode-coupling theory. For both the chains and the dumbbell, also orientational autocorrelation functions are calculated and for the dumbbell time series for the time evolution of linear dichroism and its autocorrelation function are studied. From both sets of data we find that both the mode-coupling critical temperature T(c) (representing the "cage effect") and the Vogel-Fulcher temperature T(0) (representing the caloric glass transition temperature) systematically increase with chain length. Furthermore, the dumbbell dynamics yields detailed information on the differences in the matrix dynamics that are caused by the chain length variation. Deviations from the Stokes-Einstein relation are discussed, and an outlook to related experiments is given.

Controlling the photoluminescence of CdSe/ZnS quantum dots with a magnetic field.

We present an investigation of the photoluminescence of CdSe/ZnS quantum dots at high light intensity and in low magnetic fields. Upon increasing the magnetic field up to 90 G, the photoluminescence intensity drops. When decreasing the magnetic field back to zero the photoluminescence drop remains present. A plausible explanation is the Zeeman splitting of defect-associated energy levels under the influence of a magnetic field. The defect-trapped electrons may then be positioned at a metastable level, thereby reducing the number of recombinations. This effect may be used to control the luminescence of quantum dots.

Analysis of the exponential character of single molecule rotational correlation functions for large and small fluorescence collection angles.

Coarse-grained molecular dynamics simulations and single molecule fluorescence microscopy experiments have been performed in order to investigate the influence of the numerical aperture (NA) of the microscope objective on the exponential character of the rotational correlation functions of probes embedded in complex matrices. The results obtained by using either a dry lens (NA=0.95) or an oil objective (NA=1.4) show that, in the moderately (simulations) and deeply (experiment) supercooled melts, the rotational (linear dichroism) correlation functions of the single molecules (SMs) exhibit a nonexponential character. Furthermore, by fitting Kohlrausch-Williams-Watt functions to the correlation curves, the stretching parameters turn out to be very similar for both types of objectives. Our results demonstrate that the nonexponentiality is intrinsic to the complex rotational dynamics of the SM in the supercooled solid and point to the validity of the use of a high NA dry lens to perform such experiments.

Single molecule probing of the glass transition phenomenon: simulations of several types of probes.

Molecular dynamics simulations of a system of short bead-spring chains containing an additional dumbbell are presented and analyzed. This system represents a coarse-grained model for a melt of short, flexible polymers containing fluorescent probe molecules at very dilute concentration. It is shown that such a system is very well suited to study aspects of the glass transition of the undercooled polymer melt via single molecule spectroscopy, which are not easily accessed by other methods. Such aspects include data which can be extracted from a study of fluctuations along a trajectory of the single molecule, probing the rugged energy landscape of the glass-forming liquid and transitions from one metabasin of this energy landscape to the next one. Such an information can be inferred from "distance maps" constructed from trajectories characterizing the translational and orientational motion of the probe. At the same time, determining autocorrelation functions along such trajectories, it is shown for several types of probes (differing in their size and/or mass within reasonable limits) that this time-averaged information of the probe is fully compatible with ensemble averaged information on the relaxation of the glass-forming matrix, accessible from bulk measurements. The analyzed quantities include the fluorescence lifetime, linear dichroism, and also various orientational correlation functions of the probe, in order to provide guidance to experimental work. Similar to earlier findings from simulations of bulk molecular fluids, deviations from the Stokes-Einstein and Stokes-Einstein-Debye relations are observed.

Fluorescence lifetime fluctuations of single molecules probe the local environment of oligomers around the glass transition temperature.

Single molecule fluorescence experiments have been performed on a BODIPY-based dye embedded in oligo(styrene) matrices to probe the density fluctuations and the relaxation dynamics of chain segments surrounding the dye molecules. The time-dependent fluorescence lifetime of the BODIPY probe was recorded as an observable for the local density fluctuations. At room temperature, the mean fraction of holes surrounding the probes is shown to be unaffected by the molecular weight in the glassy state. In contrast, the free volume increases significantly in the supercooled regime. These observations are discussed in the framework of the entropic theories of the glass transition.

Fluorescence lifetime of a single molecule as an observable of meta-basin dynamics in fluids near the glass transition.

Using single molecule spectroscopy, we show that the fluorescence lifetime trajectories of single probe molecules embedded in a glass-forming polymer melt exhibit strong fluctuations of a hopping character. Using molecular dynamics simulations targeted to explain these experimental observations, we show that the lifetime fluctuations correlate strongly with the average square displacement function of the matrix particles. The latter observable is a direct probe of the meta-basin transitions in the potential energy landscape of glass-forming liquids. We thus show here that single molecule experiments can provide detailed microscopic information on system properties that hitherto have been accessible via computer simulations only.

Fluorescence lifetime fluctuations of single molecules probe local density fluctuations in disordered media: a bulk approach.

We investigated the nanometer scale mobility of polymers in the glassy state by monitoring the dynamics of embedded single fluorophores. Recently we reported on fluorescence lifetime fluctuations which reflect the segmental rearrangement dynamics of the polymer in the surroundings of the single molecule probe. Here we focus on the nature of these fluorescence lifetime fluctuations. First the potential role of quenching and molecular conformational changes is discussed. Next we concentrate on the influence of the radiative density of states on the spontaneous emission of individual dye molecules embedded in a polymer. To this end we present a theory connecting the effective-medium theory to a cell-hole model, originating from the Simha-Somcynsky free-volume theory. The relation between the derived distributions of free volume and fluorescence lifetime allows one to determine the number of segments involved in the local rearrangement directly from experimental data. Results for two different polymers as a function of temperature are presented.

Single molecule lifetime fluctuations reveal segmental dynamics in polymers.

We present a single molecule fluorescence study that allows one to probe the nanoscale segmental dynamics in amorphous polymer matrices. By recording single molecular lifetime trajectories of embedded fluorophores, peculiar excursions towards longer lifetimes are observed. The asymmetric response is shown to reflect variations in the photonic mode density as a result of the local density fluctuations of the surrounding polymer. We determine the number of polymer segments involved in a local segmental rearrangement volume around the probe. A common decrease of the number of segments with temperature is found for both investigated polymers, poly(styrene) and poly(isobutylmethacrylate). Our novel approach will prove powerful for the understanding of the nanoscale rearrangements in functional polymers.