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111.
Free radicals are generated in liquid solutions by harmonically modulated photolysis of suitable substrates. Harmonic analysis of the absorbance as functions of wavelength and modulation frequency yields the optical spectra and the decay kinetics of the transient species. The experimental technique and the analysis are described in detail. Results on t-butyl, 2-propyl and benzyl radicals generated by photolysis of the corresponding dialkyl resp. dibenzyl ketones are reported. They confirm previous spectral assignments and show that the termination reactions are diffusion controlled. 相似文献
112.
Hanns Fischer 《Hyperfine Interactions》1984,19(1-4):751-770
Muonium-substituted organic free radicals are observed by muon spin rotation when positive muons are stopped in liquid unsaturated compounds. From muon precession frequencies in high external magnetic fields the isotropic muon-electron hyperfine coupling constants are determined. They lead to radical structure assignments. Results of a variety of projects are described which show thatSR can successfully complement conventional physical methods of free radical chemistry: A study of the temperature dependence of the coupling constants of isotopically substituted ethyl radicals yields information on structure and barriers to internal rotation. Rate constants for several radical reactions are extracted from the damping of theSR signals, in particular for unimolecular rearrangements and cis-trans-isomerizations. The theory for the analysis for the case of reversible site exchange is outlined.All results described here were obtained by E. Roduner, P. Burkhard and W. Strub of this laboratory, and B. Webster, M. Ramos and D. McKenna of the University of Glasgow. We all appreciate support from the Swiss National Foundation for Scientific Research, the National Institut for Scientific Investigations of Portugal, the Carnegie Trust for the Universities of Scotland, the Royal Society London and SIN. 相似文献
113.
M. Althoff W. Braunschweig F.J. Kirschfink H.-U. Martyn P. Rosskamp D. Schmitz H. Siebke W. Wallraff J. Eisenmann H.M. Fischer H. Hartmann A. Jocksch G. Knop H. Kolanoski H. Kück V. Mertens R. Wedemeyer G. Zobernig 《Physics letters. [Part B]》1984,149(6):524-532
We have determined the average lifetime of hadrons containing b quarks produced in e+e? annihilation to be . Our method uses charged decay products from both non-leptonic and semileptonic decay modes. 相似文献
114.
K. H. Fischer 《Zeitschrift für Physik B Condensed Matter》1984,55(4):317-324
The dynamics of ann-component vector spin glass with infinite range interactions are investigated near and above the Gabay-Toulouse (GT) line. The local transverse susceptibility
T
for 0 varies along the whole GT lineT
c1
(H) as
v
, with a field and temperature independent critical exponentv=1/2. The longitudinal susceptibility
L
() remains analytic for all (T, H)T
c1
(H), except for a cross-over fromv=1 tov=1/2 forH0 at the freezing temperatureT=T
f
. The dynamic susceptibilities
T
() and
L
() are already coupled above the GT line via self-energy terms. BelowT
c1
(H), this coupling is strongly enhanced by other mechanisms. 相似文献
115.
Low-temperature photoluminescence measurements on nominally undoped AlxGa1–xAs/GaAs quantum well heterostructures (QWHs) grown by molecular beam epitaxy (MBE) exemplified the exclusivelyintrinsic free-exciton nature of the luminescence under moderate excitation conditions. Neither any spectroscopic evidence for alloy clustering in the AlxGa1–xAs barriers nor any extrinsic luminescence due to recombination with residual acceptors has been detected in single and double QWHs when grown at 670 °C under optimized MBE growth conditions. Carrier confinement in AlxGa1–xAs/GaAs QWHs starts at a well width ofL
z30 nm when x0.25. The minor average well thickness fluctuation ofL
z=4×10–2nm as determined from the excitonic halfwidth allowed the realization of well widths as low asL
z=1 nm and thus a shift of the free-exciton line as high as 2.01 eV which is close to the conduction band edge of the employed Al0.43Ga0.57As confinement layer. The measurements further revealed a strongly enhanced luminescence efficiency of the quantum wells as compared to bulk material which is caused by the modified exciton transition probabilities due to carrier localization. 相似文献
116.
Nominally undoped AlxGa1–xAs grown by molecular beam epitaxy from As4 species at elevated substrate temperatures of 670°C exhibits well-resolved excitonic fine structure in the low-temperature photoluminescence spectra, if the effective As-to-(Al+Ga) flux ratio on the growth surface is kept within a rather narrow range of clearly As-stabilized conditions. In contrast to previous results on AlxGa1–xAs of composition 0.15not to shift in energy by changing the excitation intensity. This implies a simple freeelectron carbon-acceptor recombination mechanism for the line without any participation of a donor. In AlxGa1–xAs of composition close to the direct-to-indirect cross-over point, two distinct LO-phonons separated by 34 and 48 meV from the (D
0,C
0) peak position at x=0.43 were observed which were before only detectable by Raman scattering experiments. The intensity of the carbon-impurity related luminescence lines in bulk-type AlxGa1–xAs and GaAs layers was found to be strongly reduced, as compared to the excitonic recombination lines, if the respective active layer was covered by a very thin confinement layer of either GaAs on top of AlxGa1–xAs or vice versa grown in the same growth cycle. 相似文献
117.
Thin layers of basic zinc carbonate can be used with good results for separation and multiple identification of carbamate and phenylurea pesticides. Five important substances could be separated by one-dimension TLC. The best results were obtained by the following developing solvents: a) benzene, b) a mixture of benzene/petroleum ether/chloroform (6∶1∶1). The substances are either recognisable in short-wave UV-light, when a fluorescence indicator (F 254 nm) is added, or in day-light, after spraying a solution of 0.1 N AgNO3 in 3 N HNO3, followed by an UV-exposure for about 4 min. 相似文献
118.
The rates of substitution of the group X in 1-X-2-naphthol-6-sulfonic acids (X = H, Cl, Br, and I) by p-chlorobenzenediazonium ions in aqueous solution have been measured. The rates of the halogenated naphthols relative to that of the parent compound (X = H) are 0.0070:0.0089:0.149 for X = Cl, Br, and I respectively. The reaction of 1-bromo-2-naphthol-6-sulfonic acid is catalysed by thiosulfate ions; the relative rate observed for this compound does not, therefore, represent the ipso factor. It is postulated that in its substitution the release of the electrofugal leaving group (Br⊕) is rate-limiting. 相似文献
119.
A first infrared pulse at frequency ν1 interacts with vibrational states in S0 and a second visible pulse at ν2 promotes the excited molecules to the S1 state from where they fluoresce. Tuning the frequency ν2 over 600 cm?1 allows the observation of a detailed spectrum which gives information on vibrational states in S0 and on vibronic states in S1 together with corresponding Franck—Condon factors. The spectra differ drastically from the common broad and featureless absorption and fluorescence bands. 相似文献
120.
Pentacarbonyl(diethylaminocarbyne)chromium tetrafluoroborate, [(CO)5− CrCNEt2]BF4 (I), reacts with PPh3 with substitution of CO and formation of trans-tetracarbonyl(diethylaminocarbyne)triphenylphosphanechromium tetra-fluoroborate, trans-[PPh3(CO)4CrCNEt2]BF4 (III). Substitution of CO by PPh3 in neutral trans-tetracarbonyl(halo)(diethylaminocarbyne)chromium complexes, trans-X(CO)4CrCNEt2 (IVa: X = Br, IVb: X = I), leads in a reversible reaction to the corresponding tricarbonyl complexes, mer-X(PPh3)(CO)3− CrNEt2 (V), PPh3 occupying the cis-position to the carbyne ligand. With PPh3 in large excess both reactions follow a first-order rate law. This as well as the activation parameters (ΔH≠ = 104–113 kJ mol−1, ΔS≠ = 64–71 J mol−1 K−1) indicate a dissociative mechanism. 相似文献