Zur molekularkinetischen Theorie der Volumen- und Enthalpierelaxation im Einfrierbereich organischer Gläser

Zusammenfassung In der vom Verfasser vorgeschlagenen molekular-kinetischen Theorie der Nachwirkungserscheinungen organischer Gl?ser im Einfrierbereich wird die Beziehung zwischen Enthalpie- und Volumenrelaxation untersucht. Die theoretischen Beziehungen werden mit den Experimenten der Volumen- und Enthalpienachwirkung an Polystyrol, Polyvinylacetat und Glucose verglichen. Die Theorie stimmt quantitativ mit den Experimenten überein, wenn der Ausgangszustand vor der Nach-wirkung beibehalten wird. Dabei werden Enthalpie- und Volumenrelaxation im Rahmen der Me?- und Auswertegenauigkeit durch die gleichen molekularen Parameter beschrieben. ?ndert man den Ausgangszustand vor der Nachwirkung, so bleibt die Theorie nur qualitativ richtig. Zur quantitativen Beschreibung dieses Effektes hat man eine ?nderung des Parameters, der die Nichtlinearit?t der Nachwirkung beschreibt, mit dem Ausgangszustand in Rechnung zu ziehen. Diese kann von der Theorie in der bisherigen Form noch nicht erkl?rt werden. Hernn Prof. Dr.F. H. Müller danke ich herzlich für die M?glichkeit, die Arbeit in seinem Institut durchführen zu k?nnen und für anregende Diskussion. Der Deutschen Forschungsgemeinschaft bin ich dankbar, da? sie mir die Untersuchungen durch ein Forschungsstipendium erm?glicht hat.     

Quantum mechanical correlation functions for the electromagnetic field and quasi-probability distribution functions

We give new formulae permitting the calculation of time ordered but otherwise arbitrary correlation functionsK of electromagnetic field operators in terms of a class of quantum mechanical quasi-probability distribution functions. This class contains among others the socalledQ- andP-functions as well as the Wigner function.     

Integrals of the motion for a nonlinear quantum oscillator

We construct and discusss explicitly time dependent integrals of the motion of non-autonomous quantum systems. Such integrals may exist even when the classical limit of the dynamics is non-integrable.     

Non-Markoffian effects in the laser

The atomic coordinates are eliminated exactly from the laser master equation with the help of a projector technique. The resulting integrodifferential equation for the field statistical operator with the kernel given correctly up to fourth order in the coupling constant is shown to be equivalent to a fourth order differential equation with respect to time. All theories footing on an “adiabatic” elimination procedure, especially the wellknown Fokker Planck equation treatment and a recently published theory containing a second order time derivative are shown to be successive approximations to our treatment. Non-Markoffian effects are discussed.     

Thermospray liquid chromatographic—mass spectrometric multi-residue determination of 128 polar pesticides in aqueous environmental samples

Thermospray (TSP) ionization was evaluated with respect to its suitability in the LC-MS determination of a broad range of pesticides. The sensitivity and the selectivity of this method for the determination of 128 pesticides having a wide range of structures and polarities were investigated. An LC separation in combination with postcolumn addition of a volatile salt solution was developed, which permits the analysis of 95 pesticides with a single LC-MS method using reversed-phase gradient caution. The retention data and TSP mass spectra of these compounds are presented. The advantages of TSP postcolumn techniques in comparison with conventional systems are discussed. The application of this method to the analysis of an environmental sample (river water) spiked with eight phenylureas is demonstrated. lie method was evaluated with respect to detection limit, linearity and reproducibility. In addition, a simple method for enhancing the structural information from TSP spectra is reported, which makes use of specific instabilities found with many pesticides. As an example, possibilities for the confirmatory analysis of carbamates are described.     

Gas flow MRI using circulating laser-polarized 129Xe.

We describe an experimental approach that combines multidimensional NMR experiments with a steadily renewed source of laser-polarized 129Xe. Using a continuous flow system to circulate the gas mixture, gas phase NMR signals of laser-polarized 129Xe can be observed with an enhancement of three to four orders of magnitude compared to the equilibrium 129Xe NMR signal. Due to the fact that the gas flow recovers the nonequilibrium 129Xe nuclear spin polarization in 0.2 to 4 s, signal accumulation on the time scale of seconds is feasible, allowing previously inaccessible phase cycling and signal manipulation. Several possible applications of MRI of laser-polarized 129Xe under continuous flow conditions are presented here. The spin density images of capillary tubes demonstrate the feasibility of imaging under continuous flow. Dynamic displacement profiles, measured by a pulsed gradient spin echo experiment, show entry flow properties of the gas passing through a constriction under laminar flow conditions. Further, dynamic displacement profiles of 129Xe, flowing through polyurethane foams with different densities and pore sizes, are presented.     

Superradiant laser: First-order phase transition and non-stationary regime

We solve the superradiant laser model in two limiting cases. First the stationary low-pumping regime is considered where a first-order phase transition in the semiclassical solution occurs. This discontinuity is smeared out in the quantum regime. Second, we solve the model in the non-stationary regime where we find a temporally periodic solution. For a certain parameter range well-separated pulses may occur. Received: 19 June 1998 / Accepted: 19 October 1998