Biomedical subjects

Gregor Diezemann

Publications and source records attributed to Gregor Diezemann.

9 recordsLinked to original sources

PubMed2006

Flexibility of phenylene oligomers revealed by single molecule spectroscopy.

The rigidity of a p-phenylene oligomer (p-terphenyl) has been investigated by single molecule confocal fluorescence microscopy. Two different rylene diimide dyes attached to the terminal positions of the oligomer allowed for wavelength selective excitation of the two chromophores. In combination with polarization modulation the spatial orientation of the transition dipoles of both end groups could be determined independently. We have analyzed 597 single molecules in two different polymer hosts, polymethylmethacrylate and Zeonex. On average we find a 22 degrees deviation from the linear gas phase geometry (T = 0 K), indicating a rather high flexibility of the p-phenylene oligomer independent of the matrix. To substantiate our experimental results, we have performed quantum chemical calculations at the density functional theory level for the molecular geometry and the electronic excitations. Our findings are in agreement with former experiments on the persistence length of poly(p-phenylenes).

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PubMed2006

Aging in a free-energy landscape model for glassy relaxation. II. Fluctuation-dissipation relations.

Several fluctuation-dissipation relations are investigated for a simple free-energy landscape model designed to describe the primary relaxation in supercooled liquids. The calculations of the response and of the correlation functions are performed for a quench from a high temperature to a low temperature. In the model, all dynamical quantities reach equilibrium after long times, but for times shorter than the re-equilibration time they do not exhibit time-translational invariance and the fluctuation-dissipation theorem is violated. Two measures for these violations are considered. One such measure is given by the slope in a plot of the integrated response versus the correlation function and another one by the so-called fluctuation-dissipation ratio. It is found that these measures do not coincide and furthermore are not independent of the dynamical variable considered in the calculation. We propose to determine the fluctuation-dissipation ratio experimentally via measurements of the deuteron spin-lattice relaxation rate and the dielectric loss.

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PubMed2006

Kerr effect as a tool for the investigation of dynamic heterogeneities.

We propose a dynamic Kerr effect experiment for the distinction between dynamic heterogeneous and homogeneous relaxations in glassy systems. The possibility of this distinction is due to the inherent nonlinearity of the Kerr effect signal. We model the slow reorientational molecular motion in supercooled liquids in terms of noninertial rotational diffusion. The Kerr effect response, consisting of two terms, is calculated for heterogeneous and for homogeneous variants of the stochastic model. It turns out that the experiment is able to distinguish between the two scenarios. We furthermore show that exchange between relatively "slow" and "fast" environments does not affect the possibility of frequency-selective modifications. It is demonstrated how information about changes in the width of the relaxation-time distribution can be obtained from experimental results.

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PubMed2005

Aging in a free-energy landscape model for glassy relaxation.

The aging properties of a simple free-energy landscape model for the primary relaxation in supercooled liquids are investigated. The intermediate scattering function and the rotational correlation functions are calculated for the generic situation of a quench from a high temperature to below the glass transition temperature. It is found that the reequilibration of molecular orientations takes longer than for translational degrees of freedom. The time scale for reequilibration is determined by that of the primary relaxation as an intrinsic property of the model.

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PubMed2005

Rotational motion in the molecular crystals meta- and ortho-carborane studied by deuteron nuclear magnetic resonance.

Spin-lattice and spin-spin-relaxation times, one- and two-dimensional spectra as well as two- and four-time correlation functions were measured for the molecular crystals ortho- and meta-carborane using deuteron nuclear magnetic resonance. It is found that in their noncubic phases these crystals exhibit highly anisotropic motions. In order to allow for a quantitative description of the motional geometry of the carboranes several stochastic models are formulated. By comparison of the model calculations with the experimental results it is found that the dynamics of these quasi-icosahedrally shaped molecules is governed by a composite reorientation process. Here the molecules perform threefold jumps around a molecule-fixed axis which itself can be tilted in four different directions with respect to a crystal-fixed axis. The tilt angle increases significantly with increasing temperature. On the basis of measurements of four-time stimulated-echo functions, implications for dynamic heterogeneity also in comparison with that of supercooled liquids are discussed.

Anisotropy↗

PubMed2005

Fluctuation-dissipation relations for Markov processes.

The fluctuation-dissipation relation is calculated for stochastic models obeying a master equation with continuous time. In the general case of a nonstationary process, there appears to be no simple relation between the response and the correlation. Also, if one considers stationary processes, the linear response cannot be expressed via time-derivatives of the correlation function alone. In this case, an additional function, which has rarely been discussed previously, is required. This so-called asymmetry depends on the two times also relevant for the response and the correlation and it vanishes under equilibrium conditions. The asymmetry can be expressed in terms of the propagators and the transition rates of the master equation but it is not related to any physical observable in an obvious way. It is found that the behavior of the asymmetry strongly depends on the nature of the dynamical variable considered in the calculation of the correlation and the response. If one is concerned with a variable which randomizes with any transition among the states of the system, the asymmetry vanishes in most cases. This is in contrast to the situation for other classes of variables. In particular, for trap models of glassy relaxation, the fluctuation-dissipation ratio strongly depends on the observable and the asymmetry plays a dominant role in the determination of this ratio also if only neutral variables are considered. Some implications of a nonvanishing asymmetry with regard to the definition of an effective temperature are discussed.

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PubMed2005

Dynamic Kerr effect responses in the terahertz range.

Dynamic Kerr effect measurements provide a simple realization of a nonlinear experiment. We propose a field-off experiment where an electric field of one or several sinusoidal cycles with frequency omega is applied to a sample in thermal equilibrium. Afterwards, the evolution of the polarizability is measured. If such an experiment is performed in the terahertz range it might provide valuable information about the low-frequency dynamics in disordered systems. We treat these dynamics in terms of a Brownian oscillator model and calculate the Kerr effect response. It is shown that frequency-selective behavior can be expected. In the interesting case of underdamped vibrational motion we find that the frequency dependence of the phonon damping can be determined from the experiment. Also the behavior of overdamped relaxational modes is discussed. For typical glassy materials we estimate the magnitude of all relevant quantities, which we believe will be helpful in experimental realizations.

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PubMed2004

Nonresonant holeburning in the Terahertz range: Brownian oscillator model.

The response to the field sequence of nonresonant hole burning, a pump-wait-probe experiment originally designed to investigate slow relaxation in complex systems, is calculated for a model of Brownian oscillators, thus including inertial effects. In the overdamped regime the model predictions are very similar to those of the purely dissipative stochastic models investigated earlier, including the possibility to discriminate between dynamic homogeneous and heterogeneous relaxation. The case of underdamped oscillations is of particular interest when low-frequency excitations in glassy systems are considered. We show that also in this situation a frequency selective modification of the response should be feasable. This means that it is possible to specifically address various parts of the spectrum. An experimental realization of nonresonant holeburning in the Terahertz regime therefore is expected to shed further light on the nature of the vibrations around the so-called boson peak.

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PubMed2003

Dynamic heterogeneities in the out-of-equilibrium dynamics of simple spherical spin models.

The response of spherical two-spin interaction models, the spherical ferromagnet (s-FM) and the spherical Sherrington-Kirkpatrick (s-SK) model, is calculated for the protocol of the so-called nonresonant hole burning (NHB) experiment for temperatures below the respective critical temperatures. It is shown that it is possible to select dynamic features in the out-of-equilibrium dynamics of both models, one of the hallmarks of dynamic heterogeneities. The behavior of the s-SK model and the s-FM model in three dimensions is very similar, showing dynamic heterogeneities in the long-time behavior, i.e., in the aging regime. The appearance of dynamic heterogeneities in the s-SK model explicitly demonstrates that these are not necessarily related to spatial heterogeneities. For the s-FM model, it is shown that the nature of the dynamic heterogeneities changes as a function of dimensionality. With the increasing dimension, the frequency selectivity of the NHB diminishes and the dynamics in the mean-field limit of the s-FM model becomes homogeneous.

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