Response properties at the dynamic water/dichloroethane liquid–liquid interface

ABSTRACT

We present a novel approach for calculating the static dielectric permittivity profile of a liquid–liquid interface (LLI) from molecular dynamics simulations. To obtain well-defined features, comparable to those observed at solid–liquid interfaces, we find it essential to reference to the instantaneous liquid–liquid interface rather than the more commonly used average Gibbs interface. We provide a coarse-grained approach for the practical definition of the instantaneous interface and present numerical results for the prototypical water/1,2-dichloroethane system. These results show that the parallel components of the dielectric permittivity tensor can be accurately extracted. In contrast, the perpendicular component does not converge to the correct bulk value at large distances from the LLI, highlighting a flaw in the regularly applied coarse-graining procedure.     

Existence of many ergodic absolutely continuous invariant measures for piecewise-expandingC 2 chaotic transformations in ℝ2 on a fixed number of partitions

Let Ω be a region in ℝⁿ and letp = P_i ) _i ^1m , be a partition ofΩ into a finite number of closed subsets having piecewise C² boundaries of finite(n - 1 )dimensional measure. Let τ:Ω→Ω be piecewise C² onP where, τ_i = τ|p_i is aC ² diffeomorphism onto its image, and expanding in the sense that there exists α > 1 such that for anyi = 1, 2,...,m ‖Dτ_i ^-1 ‖ < α^-1, where Dτ_i ^-1 is the derivative matrixτ _i ^- 1 and |‖·‖ is the Euclidean matrix norm. By means of an example, we will show that the simple bound of one-dimensional dynamics cannot be generalized to higher dimensions. In fact, we will construct a piecewise expanding C² transformation on a fixed partition with a finite number of elements in ℝ², but which has an arbitrarily large number of ergodic, absolutely continuous invariant measures     

Growth and decay of the Pd(1 1 1)-Pd5O4 surface oxide: Pressure-dependent kinetics and structural aspects

Growth and decomposition of the Pd₅O₄ surface oxide on Pd(1 1 1) were studied at sample temperatures between 573 and 683 K and O₂ gas pressures between 10⁻⁷ and 6 × 10⁻⁵ mbar, by means of an effusive O₂ beam from a capillary array doser, scanning tunnelling microscopy (STM) and thermal desorption spectrometry (TDS). Exposures beyond the p(2 × 2)O adlayer (saturation coverage 0.25) at 683 K (near thermodynamic equilibrium with respect to Pd₅O₄ surface oxide formation) lead to incorporation of additional oxygen into the surface. To initiate the incorporation, a critical pressure beyond the thermodynamic stability limit of the surface oxide is required. This thermodynamic stability limit is near 8.9 × 10⁻⁶ mbar at 683 K, in good agreement with calculations by density functional theory. A controlled kinetic study was feasible by generating nuclei by only a short O₂ pressure pulse and then following further growth kinetics in the lower (10⁻⁶ mbar) pressure range.Growth of the surface oxide layer at a lower temperature (573 K) studied by STM is characterized by a high degree of heterogeneity. Among various metastable local structures, a seam of disordered oxide formed at the step edges is a common structural feature characteristic of initial oxide growth. Further oxide nucleation appears to be favoured along the interface between the p(2 × 2)O structure and these disordered seams. Among the intermediate phases one specifically stable phase was detected both during growth and decomposition of the Pd₅O₄ layer. It is hexagonal with a distance of about 0.62 nm between the protrusions. Its well-ordered form is a superstructure.Isothermal decay of the Pd₅O₄ oxide layer at 693 K involves at first a rearrangement into the structure, indicating its high-temperature stability. This structure can break up into small clusters of uniform size and leaves a free metal surface area covered by a p(2 × 2)O adlayer. The rate of desorption increases autocatalytically with increasing phase boundary metal-oxide. We propose that at close-to-equilibrium conditions (693 K) surface oxide growth and decay occur via this intermediate structure.     

Relaxation of hyperpolarized 129Xe in a deflating polymer bag

In magnetic resonance imaging with hyperpolarized (HP) noble gases, data is often acquired during prolonged gas delivery from a storage reservoir. However, little is known about the extent to which relaxation within the reservoir will limit the useful acquisition time. For quantitative characterization, 129Xe relaxation was studied in a bag made of polyvinyl fluoride (Tedlar). Particular emphasis was on wall relaxation, as this mechanism is expected to dominate. The HP 129Xe magnetization dynamics in the deflating bag were accurately described by a model assuming dissolution of Xe in the polymer matrix and dipolar relaxation with neighboring nuclear spins. In particular, the wall relaxation rate changed linearly with the surface-to-volume ratio and exhibited a relaxivity of κ=0.392±0.008 cm/h, which is in reasonable agreement with κ=0.331±0.051 cm/h measured in a static Tedlar bag. Estimates for the bulk gas-phase 129Xe relaxation yielded T1bulk=2.55±0.22 h, which is dominated by intrinsic Xe-Xe relaxation, with small additional contributions from magnetic field inhomogeneities and oxygen-induced relaxation. Calculations based on these findings indicate that relaxation may limit HP 129Xe experiments when slow gas delivery rates are employed as, for example, in mouse imaging or vascular infusion experiments.     

Morphological predictability and acoustic duration of interfixes in Dutch compounds

This study explores the effects of informational redundancy, as carried by a word's morphological paradigmatic structure, on acoustic duration in read aloud speech. The hypothesis that the more predictable a linguistic unit is, the less salient its realization, was tested on the basis of the acoustic duration of interfixes in Dutch compounds in two datasets: One for the interfix -s- (1155 tokens) and one for the interfix -e(n)- (742 tokens). Both datasets show that the more probable the interfix is, given the compound and its constituents, the longer it is realized. These findings run counter to the predictions of information-theoretical approaches and can be resolved by the Paradigmatic Signal Enhancement Hypothesis. This hypothesis argues that whenever selection of an element from alternatives is probabilistic, the element's duration is predicted by the amount of paradigmatic support for the element: The most likely alternative in the paradigm of selection is realized longer.     

Assessment of mitral regurgitation by magnetic resonance imaging

To evaluate the potential of magnetic resonance imaging (MRI) in detection and quantification of mitral regurgitation, 26 pts. with echocardiographically or angiographically documented mitral regurgitation were examined using a 0.5 Tesla superconducting magnet. In each patient a multislice-multiphase study in a sagittal-coronal double angulated projection (four-chamber view equivalent) was performed to assess left and right ventricular volumes, ejection fraction and regurgitant fraction. Additionally a blood flow sensitive cine-study (fast field echo: FFE) was done to visualize direction and area of regurgitant jet. MRI data were compared with quantitative and qualitative assessment of mitral regurgitation by angiography, 2D echocardiography, Doppler sonography and color flow mapping. Using the FFE mode MRI was able to detect the regurgitant jet as a typical signal loss within the left atrium in all patients. The ratio of regurgitant jet area/left atrium area as determined by MRI showed a correlation with a comparable ratio from color Doppler sonography of R = 0.87 (p < 0.001). There was also good agreement in semiquantitative grading of mitral regurgitation between MRI and angiography (R = 0.77, p < 0.001). The determination of left and right ventricular stroke volume allowed the calculation of the regurgitant fraction, which showed a correlation with invasively determined regurgitation fraction of R = 0.84 (p < 0.001). These data provide additional information that MRI may be useful as a noninvasive technique to detect and quantify mitral regurgitation.     

F-18-FDG uptake is a reliable predictory of functional recovery of akinetic but viable infarct regions as defined by magnetic resonance imaging before and after revascularization

Identification of akinetic but viable myocardium is important for the selection of patients for coronary revascularization. In order to assess predictive values of end-diastolic wall thickness and dobutamine induced wall thickening obtained by magnetic resonance imaging (MRI) and [18F]Fluorodeoxyglucose uptake assessed by positron emission tomography (F-18-FDG-PET), these parameters were compared to recovery of left ventricular function after successful revascularization. Forty patients with chronic myocardial infarction and regional a- or dyskinesia by ventriculography underwent rest- and dobutamine-MRI studies (10 microg dobutamine/kg body weight/min) and F-18-FDG-PET. Viability of the infarct region was considered to be present if; 1) end-diastolic wall thickness was > or =5.5 mm; 2) dobutamine induced wall thickening > or =2 mm could be measured; and 3) normalized F-18-FDG-uptake was > or =50% in > or =50% of akinetic segments. Preserved end-diastolic wall thickness was found in 32/40 patients, functional improvement during dobutamine infusion in 26/40 patients and preserved F-18-FDG-uptake in 29/40 patients. After revascularization regional left ventricular function improved in 25/40 patients. Positive and negative predictive values and diagnostic accuracy were 78%, 100%, and 83% for preserved end-diastolic wall thickness, 92%, 93%, and 93% for dobutamine inducible contraction reserve and 86%, 100%, and 90% for preserved F-18-FDG-uptake. Quantitative assessment of dobutamine induced systolic wall thickening by MRI and F-18-FDG-uptake by PET are highly accurate techniques for the identification of viable myocardium and prediction of functional recovery after successful revascularization. Preserved end-diastolic wall thickness results in an overestimation of viable myocardium compared to functional improvement, but wall thickness <5.5 mm excludes recovery of regional function.     

Surface termination of BaTiO3 (001) single crystals: A combined electron spectroscopic and theoretical study

The surface termination of oxide surfaces is of crucial importance for the growth of a second material like metals or other oxides. In this study we have investigated the surface of a BaTiO₃ (001) single crystal during sample preparation by various electron spectroscopic methods. It is shown by X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS) and metastable induced electron spectroscopy (MIES) that during sputtering a Ba rich overlayer is formed, in which the Ba²⁺ ions are under coordinated. Below this layer, an oxygen deficient BaTiO₃ layer is found. During annealing, we observe the reformation of the crystalline structure. UP and MIE spectra provide clear evidence of a BaO terminated surface. X-ray photoelectron diffraction studies support this result, comparing recorded polar angle scans with calculated intensity modulations using multiple scattering cluster models.