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51.
Dirk Welsch 《Annalen der Physik》1972,483(3):221-230
Two kinds of stationary RAMAN oscillators are investigated theoretically for molecular crystals. The calculations are done firstly for the generation of one first order anti-STOKES mode and secondly for the generation of one second order STOKES mode. By using a quantum theoretical model described in an earlier paper for treatment of molecular crystals RAMAN scattering is assumed to be polariton scattering. Within this framework coupled nonlinear equations for the polariton operators of the excited modes are derived, stationary occupation numbers for the different modes and threshold conditions are calculated. The influence of phase fluctuations of the pump wave on the line widths of the RAMAN modes are investigated. 相似文献
52.
Swelling of the polyimide coating of fused-silica capillaries in acetonitrile-containing buffers was found to be the reason for several problems in capillary electrophoresis (CE) and capillary electrochromatography (CEC). Scanning electron microscopy photographs of the ends of raw fused-silica tubing showed that the coating becomes soft and increases its volume after longer contact with such buffers. As a consequence, separation efficiency can deteriorate, the capillary ends can clog or break off. To prevent swelling of the polyimide coating, fused-silica capillaries used in CE or CEC were heated at 300 degrees C for a longer period of time which improved their long-term stability in comparison to raw fused-silica tubing. 相似文献
53.
Applying the recently developed formalism of quantum-state transformation of light at absorbing dielectric four-port devices [5], we calculate the quantum state of the outgoing modes of a two-mode squeezed vacuum transmitted through optical fibers of given extinction coefficients. Using the Peres-Horodecki separability criterion for continuous variable systems [4], we then compute both the maximal length of transmission of a two-mode squeezed vacuum through an absorbing system for which the transmitted state is still inseparable and the maximal gain for which inseparability can be observed in an amplifying setup. Finally, we estimate an upper bound of the entanglement preserved after transmission through an absorbing system. The results show that the characteristic length of entanglement degradation drastically decreases with increasing strength of squeezing. 相似文献
54.
Sebastian J. Welsch Michael UmkehrerGünther Ross Jürgen KolbChristoph Burdack Ludger A. Wessjohann 《Tetrahedron letters》2011,52(47):6295-6297
A variety of 1,6-enynes were synthesized by an Ugi-reaction and further elaborated by a PdII/IV catalyzed oxidative cyclization to produce N-substituted 3-aza-bicyclo[3.1.0]hexan-2-ones. Different substitution patterns were tested to examine the scope and limitations of the amide tethered substrates. 相似文献
55.
M. R. F. Siggel-King A. Papash H. Knudsen M. Holzscheiter C. P. Welsch 《Hyperfine Interactions》2011,199(1-3):311-319
There is a strong need to push forward developments in the storage and control of ultra-low-energy antiproton beams to enable important scientific research. To this end, a small electrostatic ring, and associated electrostatic acceleration section, is being designed and developed by the QUASAR group. The ring will be placed on the MUSASHI beamline at the CERN-AD. It will serve as a prototype for the future ultra-low energy storage ring (USR), to be integrated at the facility for low-energy antiproton and ion research (FLAIR) and will enable various components of the USR to be tested and optimised. A reaction microscope will be integrated in the ring to enable partial ionisation cross section measurements to be made. This small recycler ring will be unique due to its combination of size, electrostatic nature and energy and type of circulating particles (ca 3?C30 keV antiprotons). A short electrostatic accelerating section is also being developed, which will be placed between the beamline and the ring to accelerate the antiprotons from the trap extraction energy (typically 250 eV) to the final required (re-circulating) energy. The AD recycler project will be described, including ring design, accelerating injection section and the inclusion of a reaction microscope and the experiments it will enable. 相似文献
56.
Welsch T Schmidtkunz C Müller B Meier F Chlup M Köhne A Lämmerhofer M Lindner W 《Analytical and bioanalytical chemistry》2007,388(8):1717-1724
A feasibility study on the fast enantioselective two-dimensional HPLC separation of racemic amino acid derivatives is presented.
The method involves the on-line coupling of a narrow-bore C18 RP column in the first dimension to a short enantioselective
column based on nonporous 1.5 μm particles modified with quinidine carbamate as chiral selector in the second dimension. Conceptually,
the system was designed to enable both time-controlled repeated transfer of fractions of the eluate and detector-controlled
transfer of selected fractions from column 1 to column 2. To avoid volume overloading of the second chiral column, a narrow-bore
reversed phase column was installed in the first dimension. Due to the fast (less than 1.5 minutes) enantiomer separation
that occurs in the second dimension, the overall analysis time for the two-dimensional separation of a mixture of nine racemic
3,5-dinitrobenzoyl amino acids was optimized at 16 minutes. 相似文献
57.
Rigorous quantum dynamics calculations of reaction rates and initial state-selected reaction probabilities of polyatomic reactions can be efficiently performed within the quantum transition state concept employing flux correlation functions and wave packet propagation utilizing the multi-configurational time-dependent Hartree approach. Here, analytical formulas and a numerical scheme extending this approach to the calculation of state-to-state reaction probabilities are presented. The formulas derived facilitate the use of three different dividing surfaces: two dividing surfaces located in the product and reactant asymptotic region facilitate full state resolution while a third dividing surface placed in the transition state region can be used to define an additional flux operator. The eigenstates of the corresponding thermal flux operator then correspond to vibrational states of the activated complex. Transforming these states to reactant and product coordinates and propagating them into the respective asymptotic region, the full scattering matrix can be obtained. To illustrate the new approach, test calculations study the D + H(2)(ν, j) → HD(ν', j') + H reaction for J = 0. 相似文献
58.
Summary The retention indices of cycloalkenes and cycloalkadienes with C6–C13 rings are determined by gas-liquid chromatography (GLC) on glass capillary columns coated with OV-1 and Ucon LB 550X and
by gas-solid chromatography (GSC) on a microcolumn packed with uncoated graphitized thermal carbon black (GTCB). Structure
— retention correlations are derived on using index differences such as HOV, HGTCB and ΔI values, considering the differences in the stereochemistry of these compounds. It is shown that the combined application
of index increments obtained in GLC and GSC provides more detailed structure informations. The value of the retention index
units agree with the most stable conformations of the alicyclic compounds.
The high value for the energy equivalent to an index unit (ΔGI.U.=4.18kJ/mol) confirmes that graphitized thermal carbon black causes much stronger dispersive interactions than any nonpolar
liquid phase.
Dedicated to Prof. Dr. E. sz. Kováts (Ecola Polytechnique Fédérale de Lausanne) on the occasion of his sixtieth birthday. 相似文献
59.
Silica gels modified with n-alkyl chains (n = 18, 30) are prepared by two different synthetic routes and are examined by variable temperature FTIR and solid-state NMR spectroscopy. HPLC measurements of SRM 869, cis/trans ss-carotene isomers and xanthophylls isomers confirm the dependence of the separation mechanism on the alkyl chain length and the synthetic routes. The determination of the silane functionality and degree of cross-linking of silane ligands on the silica surface is achieved by 29Si CP/MAS NMR measurements. The structural order and mobility of the alkyl chains are investigated by means of variable temperature 13C CP/MAS NMR measurements. Variable temperature FTIR studies are performed where conformational order and flexibility of the alkyl chains in C18 and C30 phases are monitored through conformational sensitive CH2 symmetric, anti-symmetric stretching and wagging modes. In addition, the chromatographic properties of the C18 and C30 phases are determined. The results derived from the FTIR, NMR and HPLC measurements are discussed in the context of the applied synthetic routes and alkyl chain lengths. 相似文献
60.
The outlier detection problem and the robust covariance estimation problem are often interchangeable. Without outliers, the classical method of maximum likelihood estimation (MLE) can be used to estimate parameters of a known distribution from observational data. When outliers are present, they dominate the log likelihood function causing the MLE estimators to be pulled toward them. Many robust statistical methods have been developed to detect outliers and to produce estimators that are robust against deviation from model assumptions. However, the existing methods suffer either from computational complexity when problem size increases or from giving up desirable properties, such as affine equivariance. An alternative approach is to design a special mathematical programming model to find the optimal weights for all the observations, such that at the optimal solution, outliers are given smaller weights and can be detected. This method produces a covariance estimator that has the following properties: First, it is affine equivariant. Second, it is computationally efficient even for large problem sizes. Third, it easy to incorporate prior beliefs into the estimator by using semi-definite programming. The accuracy of this method is tested for different contamination models, including recently proposed ones. The method is not only faster than the Fast-MCD method for high dimensional data but also has reasonable accuracy for the tested cases. 相似文献