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21.
NH chemical shift temperature coefficients have been measured in a large series of N-substituted-3-piperidinethiopropionamides in which the NN distances are short but of varied length, as well as in a couple of the corresponding amides and in some simpler amides and thioamides. Geometries are calculated by means of ab initio DFT methods. The N-substituted-3-piperidinethiopropionamides show in most cases strong intramolecular N–HN hydrogen bonds according to IR spectra and ab initio calculations. For compounds with rather short NN distances the S=C–N–H moiety is non-planar. Dihedral angles as small as 160° are found. The NH chemical shift coefficients measured in non-polar solvents in all the N-substituted-3-piperidinethiopropionamides are more negative (−8 to −17 ppb/K) than in non-hydrogen bonded thioamides. For the latter in non-polar solvents like CDCl3 and toluene the temperature coefficients are as small as −1 to −4 ppb/K. The large negative effects can be related not only to the non-planarity of the thioamide group in a way that the more pronounced the non-planarity the more negative the temperature coefficients, but also to strong hydrogen bonding and the fact that the acceptor is a nitrogen. For similar amides with non-planar amide groups and nitrogen acceptor large negative temperature coefficients are likewise seen. In polar solvents like DMF the effects in simple thioamides are uniform and close to −6 ppb/K, whereas in the more complex compound like 4p(t) the temperature coefficient is close to 0. An essential feature of measuring temperature coefficients of compounds without strong intramolecular hydrogen bonds in non-polar solvents and at low temperatures is to keep the concentration low enough to avoid dimerisation. 相似文献
22.
Searching in trees 总被引:1,自引:0,他引:1
Frank Recker 《Discrete Applied Mathematics》2004,140(1-3):169-183
In (Discrete Math. 17 (1977)181) Rivest introduced the search complexity of binary trees and proved that among all binary trees with a fixed search complexity the smallest ones are the so-called Fibonacci trees. This result is extended for q-trees. The structure of the smallest q-trees is again Fibonacci-like but more complicated than in the binary case. In addition an upper bound for the asymptotic growth of these trees is given. 相似文献
23.
We examine certain special features exhibited by various classes of linear operators acting in a hereditarily indecomposable
Banach space. For instance, we show that the family of all Riesz operators in a H.I. space forms a closed, 2-sided ideal.
We also give further characterizations of the class of scalar-type spectral operators (to those already given in [16]). The
final section discusses some properties of the spectral maximal spaces of (necessarily decomposable) linear operators in such
spaces.
Conferenza tenuta il 16 settembre 1997
The support of the German Academic Exchange Scheme (DAAD) is gratefully acknowledged 相似文献
24.
A. Hoffknecht O. Uwira A. Frank S. Schennach W. Spies M. Wagner S. Schippers A. Müller R. Becker M. Kleinod N. Angert P.H. Mokler 《Hyperfine Interactions》1998,114(1-4):257-261
The origin of the widely observed enhancement of rates for electron-ion recombination at very low energies is still unknown.
We investigated the recombination of Au25+ with free electrons in a merged-beams experiment at the UNILAC accelerator of the GSI in Darmstadt. At E
rel= 0 eV we found an enormous enhancement factor of 365 compared to the theory of radiative recombination. An increase of the
electron density by a factor of 10 had not much influence on the measured rate coefficient.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
25.
Frank C. Spano 《Chemical physics letters》1994,220(6):365-370
A nonperturbative theory for the pump—probe absorption spectrum of Frenkel exciton chains is developed in the early saturation regime. In the J-aggregate configuration, the entire spectrum is blue-shifted in proportion to the pump intensity. The results are in good agreement with experiment. 相似文献
26.
We construct cellular homotopy theories for categories of simplicial presheaves on small Grothendieck sites and discuss applications to the motivic homotopy category of Morel and Voevodsky. 相似文献
27.
Frank H.G.M. Wijnands Charles G. Crookes Paul M. Charles Richard M. Ash Ian F. Lealman Michael J. Robertson Anthony E. Kelly Kevin A. Williams Aeneas B. Massara Richard V. Penty Ian H. White 《Optical and Quantum Electronics》2002,34(10):959-973
An anomalous modulation in the wavelength spectrum has been observed in lasers with spot-size converters. This intensity modulation is shown to be caused by beating between the fundamental lasing mode and radiation modes in the taper. This results in a periodic modulation in the net gain spectrum, which causes wavelength jumps between adjacent net gain maxima, and a drive current dependent spectral width that is expected to affect system performance. The amplitude of this spectral modulation is reduced significantly by either using an angled rear-facet which reflects the beating radiation modes away from the laser axis, or by using a nonlinear, adiabatic taper. 相似文献
28.
29.
Frank Morgan 《Annals of Global Analysis and Geometry》2006,30(1):73-79
In a product M
1 × M
2 of Riemannian manifolds, the least perimeter required to enclose given volume among general regions is at least 1/√ 2 times that among regions of product form, assuming that the isoperimetric profiles of M
1 and M
2 are concave. This result sharpens earlier work of Grigor'yan, generalizes results of Bollobás and Leader and of Barthe, and yields a lower bound on the Cheeger isoperimetric constant of a product. 相似文献
30.
We have characterized multidielectric scaled SONOS nonvolatile memory structures with the quasi-static linear voltage ramp (LVR) technique and dynamic pulse measurements. We have formulated physically-based ERASE/WRITE and retention methods with deep level amphoteric traps which capture and emit carriers to the bands in the silicon nitride film. Amphoteric trap parameters are extracted by the LVR technique. ERASE/WRITE and retention amphoteric trap model simulations agree well with the experimental dynamic pulse measurements. Experimental scaled SONOS structures have been fabricated with tunnel oxide XOT=20 Å, nitride XN=30 Å and blocking oxide XOB=55 Å and demonstrated a static flatband shift of 3.6 V with ±5 V programming voltages. These structures may be used as the nonvolatile memory element in high density VLSI circuits. 相似文献