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101.
102.
Wind M Brombacher L Heuer A Graf R Spiess HW 《Solid state nuclear magnetic resonance》2005,27(1-2):132-139
Geometry and time scale of structural relaxation of poly(n-alkylmethacrylates) above the glass transition is studied by temperature dependent one- and two-dimensional 13C-NMR spectroscopy. The geometry of the isotropization of the polymer backbone as deduced from detailed analysis of spectral line shapes is identified as random angular jumps. Analysis of echo decays confirms that at a given temperature this isotropization can adequately be described with a single correlation time. The results are discussed in terms of conformational memory and local structure recently identified in these polymeric glasses. 相似文献
103.
Novitchi G Riblet F Helm L Scopelliti R Gulea A Merbach AE 《Magnetic resonance in chemistry : MRC》2004,42(9):801-806
The cobalt(II) complexes [CoL2(R2-Py)2] (1-4) where HLA = 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione, R2-Py = 4-methylpyridine (1), HLB = 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione, R2-Py = 4-methylpyridine (2), 4-phenylpyridine (3) and S-(-)-1-(4-pyridyl)ethanol (4) were prepared by two-step reactions. X-ray structure analysis of [CoLA2(CH3-Py)2] revealed the {trans(N)-trans(CF3)-trans} configuration for the complex obtained by crystallization from ethanol. A dynamic equilibrium between the five possible stereoisomers was observed for each complex 1-4 in solution by 19F NMR spectroscopy. The criteria used for full NMR assignment (180-265 K) include comparison of integral ratios, cis(N) and trans(N) differentiation in presence of the chiral amine [S-(-)-1-(4-pyridyl)ethanol], effect of solvent polarity on the relative stabilities of the five isomers and observation of trans influences in a mixture of complexes. Thermodynamic parameters for the equilibria between the isomers of 2 in CD2Cl2 (DeltaHi,j, DeltaSi,j and Ki,j) were obtained from signal integrals. The two trans(N) isomers are slightly more stable than the three cis(N) isomers at low temperature [DeltaGdegreesi,j (max) = 2.8 kJ mol(-1) at 179.8 K], but this stability difference almost vanishes with increasing temperature [DeltaGdegreesi,j (max) = 1.0 kJ mol(-1) at 265.0 K]. The values found for DeltaHdegreesi,j are relatively small and largely entropy compensated. 相似文献
104.
Buser M Frommhold L Gustafsson M Moraldi M Champagne MH Hunt KL 《The Journal of chemical physics》2004,121(6):2617-2621
Quantum line shape calculations of the rototranslational enhancement spectra of nitrogen-methane gaseous mixtures are reported. The calculations are based on a recent theoretical dipole function for interacting N(2) and CH(4) molecules, which accounts for the long-range induction mechanisms: multipolar inductions and dispersion force-induced dipoles. Multipolar induction alone was often found to approximate the actual dipole surfaces of pairs of interacting linear molecules reasonably well. However, in the case of the N(2)-CH(4) pair, the absorption spectra calculated with such a dipole function still show a substantial intensity defect at the high frequencies (>250 cm(-1)) when compared to existing measurements at temperatures from 126 to 297 K, much as was previously reported. 相似文献
105.
Diffraction of monochromatic light on a grating leads to the attenuation of the transmitted beam of diffraction order zero. In the case of a thick grating the diffraction efficiency, and hence the effective attenuation coefficient, is a fast-varying function of the Bragg mismatch angle. According to Kramers-Kronig theory, the transmitted beam encounters a phase shift that also depends on the mismatch angle. This phase shift is measured for holographic gratings in a photoaddressable block copolymer and compared with analytical calculations. 相似文献
106.
Determination of the phase or phase derivative from interferometric fringe patterns is an important task in optical interferometry. The use of wavelet ridges was recently shown to be an effective method for phase retrieval from a single fringe pattern. One necessary requirement in this method is the need for carrier frequency. In cases when carrier frequency is not available, the novel phase-shifting windowed Fourier ridges method can be used. Phase derivatives with the proper sign can be directly retrieved even in the presence of noise. An application for curvature determination from speckle shearographic fringes demonstrates the effectiveness of the method. 相似文献
107.
Lothar von Wolfersdorf 《Applicable analysis》2013,92(1-4):309-319
Two basic inverse problems for determining the constitutive relation in an attenuating medium from given absorption behavior of plane waves in the medium are dealt with in the frequency domain by methods of complex analysis. In particular the case of a prescribed constant internal friction function over the seismic frequencies is considered in detail. 相似文献
108.
Predicting potential changes in groundwater salinity in low-lying coastal regions due to climate change is important, where coastal vegetation is abundant, succession competition between halophytes and glycophytes plays a significant role in the salinity budget. Sea level rise enhances salinity intrusion, contributing an additional dimension to vegetation competition. A new simulation model known as mangrove-hardwood hammock model coupled with saturated-unsaturated transport (MANTRA) has recently been developed by the authors to simulate groundwater salinity regimes in the presence of vegetation competition, subject to climate change. MANTRA is based upon linking two existing Unites States geological survey (USGS) simulation models known as mangrove-hardwood hammock model (MANHAM) and saturated-unsaturated transport (SUTRA). MANHAM simulates the evolution of vegetation succession subject to changing groundwater salinity. SUTRA simulates saturated and unsaturated transport of solutes and salinity in groundwater given sea salinity. MANTRA improves the simulation robustness to simultaneously simulate groundwater hydrology, salinity and coastal vegetation succession subject to sea level rise. Some simulation results will be presented to demonstrate the impact of sea level rise on coastal vegetation succession and groundwater salinity. 相似文献
109.
Lothar Heffter 《Archiv der Mathematik》1948,1(1):77-79
Ohne Zusammenfassung 相似文献
110.
Peter Rapta Krzysztof R. Idzik Vladimír Lukeš Rainer Beckert Lothar Dunsch 《Electrochemistry communications》2010,12(4):513-516
The role of the chemical structure in an alternative charge stabilisation and a changing reactivity of star-shaped compounds with a central triazine ring linked to aryl groups like thiophene, furan or ethylenedioxythiophene synthesized by a Stille cross-coupling procedure, is followed by spectroelectrochemical measurements. While cathodic reduction leads to stable anion radicals with a delocalised spin on the central triazine moiety, dimerisation and oligomerisation occurs upon anodic oxidation. The stability of the charged states in the polymer film increased substantially using an EDOT (3,4-ethylenedioxythiophene) side group. The location of the charged states on the molecules has been proved by computations. These star-shaped molecules are excellent model structures for studies of the competition of dimerisation and oligomerisation processes based on the variation of the electron and spin distribution in the molecules. 相似文献