Depolarized light scattering spectra of molecular liquids: Described in terms of mode coupling theory.

Depolarized light scattering spectra of eight molecular liquids as obtained from applying tandem-Fabry-Pérot interferometry and double monochromator are analyzed in the frame work of the mode coupling theory (MCT). The susceptibility spectra are fitted to the numerical solution of the schematic F12 model of MCT and the validity of the asymptotic laws is discussed. The model is able to quantitatively describe the spectra up to the boiling point, where the main (structural) relaxation and the contribution of the microscopic (vibrational) dynamics essentially merge, and down to the moderately super-cooled liquid where glassy dynamics establishes. The changes of the spectra with temperature are mapped to only two control parameters, which show a smooth variation with temperature. Strong correlation between experimental stretching parameters and extrapolated values from the model is found. The numerical solutions are extrapolated down to Tc, where the asymptotic scaling laws can be applied. Although the spectra apparently follow scaling relations, the application of the asymptotic laws usually overestimates Tc by up to 12 K. In all the cases, the experimental spectra are outside the applicability regime of the asymptotic laws. This is explained by more or less strong vibrational contributions. Within a phenomenological approach which extends the spectral analysis down to Tg and which allows for separating fast and slow dynamics, the strength of the fast dynamics 1 - frel is revealed. It shows the cusp-like anomaly predicted by MCT; yet, the corresponding critical temperature is significantly higher than that derived from the F12 model. In addition, we demonstrate that close to Tg, the susceptibility minimum is controlled by the interplay of the excess wing and the fast dynamics contribution.

Relaxation stretching, fast dynamics, and activation energy: a comparison of molecular and ionic liquids as revealed by depolarized light scattering.

Depolarized light scattering (DLS) spectra of a series of 16 molecular and 6 room temperature ionic liquids are investigated by applying tandem-Fabry-Pérot interferometry, double monochromator, and photon correlation spectroscopy. Temperatures up to well above the melting point, in some cases, even up to the boiling point, are covered, and all liquids can be supercooled. The accessed time constants are between 1 ps and 10 ns; in some cases, even longer times are reached. The susceptibility spectra and likewise the corresponding reorientational correlation functions are characterized by stretching parameter ß(CD) (0.32-0.80) for the long-time decay (α-process), strength of fast dynamics 1 - f, and time scale at shortest times expressed by k(B)T/I* with the apparent quantity I* reflecting essentially inertia effects. An additional (intermediate) power-law regime (or excess wing in the frequency domain) between fast dynamics and the α-process has to be taken into account. For a given system the spectral parameters are virtually temperature independent up to the boiling point, i.e., frequency-temperature superposition applies for the α-process. Among the liquids, the quantity I* correlates with molecular mass, and the larger 1 - f, the smaller the inertial quantity I*. No correlation among 1 - f and ß(CD) is revealed. Testing for correlation of ß(CD) or 1 - f with parameters describing the temperature dependence of the correlation time τ(α), namely, high-temperature activation energy E(∞), fragility m, or glass transition temperature T(g), no significant correlation is found. Regarding molecular vs ionic liquids, no relevant difference in the evolution of their DLS spectra is observed.

Dynamics of asymmetric binary glass formers. I. A dielectric and nuclear magnetic resonance spectroscopy study.

Dielectric spectroscopy as well as (2)H and (31)P nuclear magnetic resonance spectroscopy (NMR) are applied to probe the component dynamics of the binary glass former tripropyl phosphate (TPP)/polystyrene (PS/PS-d3) in the full concentration (cTPP) range. In addition, depolarized light scattering and differential scanning calorimetry experiments are performed. Two glass transition temperatures are found: Tg 1(cTPP) reflects PS dynamics and shows a monotonic plasticizer effect, while the lower Tg 2(cTPP) exhibits a maximum and is attributed to (faster) TPP dynamics, occurring in a slowly moving or immobilized PS matrix. Dielectric spectroscopy probing solely TPP identifies two different time scales, which are attributed to two sub-ensembles. One of them, again, shows fast TPP dynamics (α2-process), the other (α1-process) displays time constants identical with those of the slow PS matrix. Upon heating the α1-fraction of TPP decreases until above some temperature Tc only a single α2-population exists. Inversely, below Tc a fraction of the TPP molecules is trapped by the PS matrix. At low cTPP the α2-relaxation does not follow frequency-temperature superposition (FTS), instead it is governed by a temperature independent distribution of activation energies leading to correlation times which follow Arrhenius laws, i.e., the α2-relaxation resembles a secondary process. Yet, (31)P NMR demonstrates that it involves isotropic reorientations of TPP molecules within a slowly moving or rigid matrix of PS. At high cTPP the super-Arrhenius temperature dependence of τ2(T), as well as FTS are recovered, known as typical of the glass transition in neat systems.

Reorientational dynamics in molecular liquids as revealed by dynamic light scattering: from boiling point to glass transition temperature.

We determine the reorientational correlation time τ of a series of molecular liquids by performing depolarized light scattering experiments (double monochromator, Fabry-Perot interferometry, and photon correlation spectroscopy). Correlation times in the range 10(-12) s-100 s are compiled, i.e., the full temperature interval between the boiling point and the glass transition temperature T(g) is covered. We focus on low-T(g) liquids for which the high-temperature limit τ ≅ 10(-12) s is easily accessed by standard spectroscopic equipment (up to 440 K). Regarding the temperature dependence three interpolation formulae of τ(T) with three parameters each are tested: (i) Vogel-Fulcher-Tammann equation, (ii) the approach recently discussed by Mauro et al. [Proc. Natl. Acad. Sci. U.S.A. 106, 19780 (2009)], and (iii) our approach decomposing the activation energy E(T) in a constant high temperature value E∞ and a "cooperative part" E(coop)(T) depending exponentially on temperature [Schmidtke et al., Phys. Rev. E 86, 041507 (2012)]. On the basis of the present data, approaches (i) and (ii) are insufficient as they do not provide the correct crossover to the high-temperature Arrhenius law clearly identified in the experimental data while approach (iii) reproduces the salient features of τ(T). It allows to discuss the temperature dependence of the liquid's dynamics in terms of a E(coop)(T)/E∞ vs. T/E∞ plot and suggests that E∞ controls the energy scale of the glass transition phenomenon.

Evolution of the dynamic susceptibility in molecular glass formers: results from light scattering, dielectric spectroscopy, and NMR.

Although broadly studied, molecular glass formers are not well investigated above their melting point. Correlation times down to 10(-12) s are easily accessible when studying low-T(g) systems by depolarized light scattering, employing a tandem-Fabry-Perot interferometer and a double monochromator. When combining these techniques with state-of-the-art photon correlation spectroscopy (PCS), broad band susceptibility spectra become accessible which can compete with those of dielectric spectroscopy (DS). Comparing the results with those from DS, optical Kerr effect, and NMR, we describe the evolution of the susceptibilities starting from the boiling point T(b) down to T(g), i.e., from simple liquid to glassy dynamics. Special attention is given to the emergence of the excess wing contribution which is also probed by PCS and which signals a crossover of the spectral evolution. The process is attributed to a small-angle precursor process of the α-relaxation, and the apparent probe dependent stretching of the α-process is explained by a probe dependent contribution of the excess wing. Upon cooling, its emergence is linked to a strong decrease of the strength of the fast dynamics which is taken as reorientational analog of the anomaly of the Debye-Waller factor. Many glass formers show in addition a slow ß-process which manifests itself rather universally in NMR, in DS, however, with different amplitudes, but not at all in PCS experiments. Finally, a three-parameter function is discussed interpolating τ(α)(T) from T(b) to T(g) by connecting high- and low-temperature dynamics.

From boiling point to glass transition temperature: transport coefficients in molecular liquids follow three-parameter scaling.

The phenomenon of the glass transition is an unresolved problem in condensed matter physics. Its prominent feature, the super-Arrhenius temperature dependence of the transport coefficients, remains a challenge to be described over the full temperature range. For a series of molecular glass formers, we combined τ(T) collected from dielectric spectroscopy and dynamic light scattering covering a range 10(-12) s < τ(T) < 10(2) s. Describing the dynamics in terms of an activation energy E(T), we distinguish a high-temperature regime characterized by an Arrhenius law with a constant activation energy E(∞) and a low-temperature regime for which E(coop)(T) ≡ E(T)-E(∞) increases exponentially while cooling. A scaling is introduced, specifically E(coop)(T)/E(∞) [proportionality] exp[-λ(T/T(A)-1)], where λ is a fragility parameter and T(A) a reference temperature proportional to E(∞). In order to describe τ(T) still the attempt time τ(∞) has to be specified. Thus, a single interaction parameter E(∞) describing the high-temperature regime together with λ controls the temperature dependence of low-temperature cooperative dynamics.

Experimental verification of quadrupole-dipole interference in spin-resolved photoionization.

We have measured the spin polarization of Xe (4p)(-1) photoelectrons after ionization with circularly polarized light at photon energies close to the ionization threshold where a resonant enhancement of quadrupole transitions has recently been predicted. At a reaction angle of 90 degrees a nonvanishing longitudinal spin polarization component of about 4% clearly indicates a quadrupole contribution to the photoexcitation. This is the first experimental evidence for the influence of nondipole transitions on the photoionization process at excitation energies much below 1 keV in an observable other than the intensity angular distribution.

Asymmetry in photoelectron emission from chiral molecules induced by circularly polarized light.

In photoionization of free, unoriented chiral molecules with circularly polarized radiation, a significant circular dichroism, i.e., an asymmetry in the forward-backward electron emission, has been observed in the photoelectron angular distribution. This leads also to an asymmetry in the momentum transfer to the photoions. The spectra for the left- and right-handed enantiomers of bromocamphor exhibit asymmetries up to several percent which vary as a function of orbital binding energy. This enantioselective effect can similarly occur for biomolecules with handedness, like amino acids, and may thus be a contributing factor related to the origin of the terrestrial biomolecular homochirality.

Sudden interchannel interaction in the Tl 6p ionization above the 5d threshold

The linear magnetic dichroism in the angular distribution of Tl 5d and 6p photoelectrons and their dynamical spin polarization have been measured between hnu = 30 and 50 eV. In contrast to the Xe 5p photoionization at the 4d threshold, our results show that above the Tl 5d threshold strong interchannel coupling effects induce a sudden increase in the asymptotic phase difference of the s and d waves for the Tl 6p ionization. This shows that the valence excitation is different for resonant (Xe 4d) and nonresonant (Tl 5d) excitation from subvalence shells.

[Health economic aspects of dental medicine consultation and expert assessment by the health insurance medical service]. / Gesundheitsäokonomische Aspekte zahnmedizinischer Beratung und Begutachtung durch den Medizinischen Dienst der Krankenversicherung.

Within one year the Statutory Health Insurance Medical Service in Lower Saxony (Germany) gave expert opinion in 2,005 cases of treatment plans in dental medicine. The legal basis and structure of organisation are described as well as professional expertising criteria. Therapeutic schemes and estimations of treatment costs were used to ascertain the socioeconomic outcome of expert evaluation expressed the by exact equivalent in terms of money value. The single expert statement valued on average 2.230,-DM (approximately 1,500 US $) for an expertise recommending rejection of treatment cost coverage.