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991.
The potential energy curve of the system Li+/He has been determined with moderately large basis sets for 0.5 ? r ? 10.0 a0 both at the SCF level and including correlation. The present SCF results predict a deeper well (?0.00248 au) at a smaller r(3.66 a0) compared with earlier calculations. Correlation deepens the well further (?0.00274 au), but pulls it inward slightly (3.63 a0). In the repulsive part the calculated curve lies above the experimental one, especially at shorter distances. A similar behavior has been noted in the systems Li+/H2, Li+/CO and Li+/N2, suggesting that the experimental determinations may underestimate the interaction in this region by 10–20%. 相似文献
992.
Cabrera JA Bieler CR Olbricht BC van der Veer WE Janda KC 《The Journal of chemical physics》2005,123(5):054311
Time- and frequency-resolved pump-probe measurements on NeBr2 have been performed to better characterize its fragmentation dynamics on the B electronic state for vibrational levels in the energy region of the transition from direct vibrational predissociation to intramolecular vibrational relaxation dynamics. Above nu'=20 of the Br2 stretching mode, it was observed that the dependence of lifetime on the vibrational quantum number deviates from the energy-gap law by leveling off in the range of 10 psE transitions of the complex. These transitions are shifted 20 cm(-1) to lower energy from the free Br2 resonances, indicating an E state Ne-Br2 bond energy of 82 cm(-1). Measurements of NeBr2 vibrational predissociation via the delta nu=-2 channel were also performed for nu'=27, 28, and 29. The closing of the delta nu=-1 channel leads to an increase in the lifetimes of these vibrational levels. A new Nd:yttrium aluminum garnet pumped dual optical parametric oscillator/optical parametric amplifier system is described that allows us to conveniently record time-delayed pump-probe spectra with 2-cm(-1) spectral resolution and 15-ps time resolution. 相似文献
993.
The basic obstacles for the general use of laser-ablation(LA)-ICP-MS in analytical laboratories are connected with its reproducibility and calibration. A mathematical relation deduced from the correlation function of the analytical signals allows the estimation of the number of craters needed for representative analyses. The procedure was applied to different samples such as manganese crusts and soils. The ion intensities of the major elements in the manganese crusts and nodules were used as internal standards, improving relative standard deviations by factors between 2 and 3. Selected samples of wood and manganese crusts were analyzed by LA-ICP-MS and the results compared with those obtained by solution ICP-MS. The agreement of the values is within the 95% confidence limits. Powdered reference materials and, in the case of wood analysis, cellulose doped with standard solutions were used for the calibration. 相似文献
994.
The isolation of (2S,1'S,2'S)-2-(2'-carboxycyclopropyl)glycine (CCG I, 2) from Blighia sapida (Akee) was achieved through column chromatography on deactivated silica gel followed by ion-exchange chromatography. A HPLC method has also been devised in order to assess the purity of the isolated product. 相似文献
995.
D. C. Aumann H. J. Born und R. Henkelmann 《Fresenius' Journal of Analytical Chemistry》1966,221(1):101-108
Zusammenfassung Der intensive Fluß schneller Neutronen, wie er von Kernreaktoren geliefert wird, kann für eine rasche und zerstörungsfreie, aktivierungs-analytische Bestimmung einer Vielzahl von Elementen verwendet werden. Bei manchen Elementen läßt sich sogar bei der Aktivierung mit schnellen Reaktorneutronen eine im Vergleich zur Aktivierungsanalyse mit thermischen Neutronen tiefere Erfassungsgrenze erreichen. Werden die Proben in einem schnellen, halbautomatischen Rohrpostsystem zum Reaktorkern befördert, können auch sehr kurzlebige Radionuklide gemessen werden. Besonders Sauerstoff läßt sich über die Kernreaktion 16O(n, p)16N sehr empfindlich bestimmen, wobei die hochenergetischen -Quanten des 7,2 sec Stickstoff-16 gemessen werden. Es können so bis zu 10 ppm Sauerstoff in vielen Arten von Analysenproben erfaßt werden. Das halbautomatische Analysensystem, das mit Hilfe einer schnellen Rohrpost die Durchführung rascher und zerstörungsfreier Aktivierungs-analysen im Forschungsreaktor München erlaubt, wird beschrieben. Die Verwendung des Systems zur Sauerstoffanalyse und die damit zusammenhängenden Probleme werden genauer besprochen.
Summary The intense fast-neutron fluxes, which are available in nuclear reactors, can be used for rapid and non-destructive activation analysis of many elements. Some elements have even superior detection limits for activation with fast reactor neutrons compared to reactor thermal-neutron activation. Short-lived radionuclides can also be measured using a fast pneumatic tube system. Oxygen can be determined by the nuclear reaction 16O(n, p)16N initiated by fast reactor neutrons counting the high-energy gamma rays of the 7.4 sec nitrogen-16. The method is suitable for determining as little as 10 ppm of oxygen in many types of analytical samples. The fast transfer system, which is used in the Munich research reactor for rapid and non-destructive activation analysis is described. The use of the transfer-system for oxygen activation analysis and problems associated with oxygen analysis are discussed.相似文献
996.
The Pd-catalyzed annulation of arynes by 2-halobiaryls and related vinylic halides provides a very efficient, high yielding synthesis of polycyclic aromatic and heteroaromatic hydrocarbons. This process appears to involve the catalytic, stepwise coupling of two very reactive substrates, an aryne and an organopalladium species, to generate excellent yields of cross-coupled products. 相似文献
997.
P. A. Beeley J. M. Brushwood M. G. Henesy M. W. Collins C. A. Haywood 《Journal of Radioanalytical and Nuclear Chemistry》1997,215(1):135-139
The measurement of16N and18F activity in the primary coolant of the JASON Argonaut reactor has been used to monitor in-core reactor power. The16N is produced by the16O(n, p)16N reaction and the 6.1 MeV photopeak was measured on-line using a BGO detector adjacent to the primary coolant circuit. These data provided a relative measure of power stability during steady state operation and a measure of linearity at different power levels. The18F is produced in the primary coolant by the18O(p, n)18F reaction and aliquots of primary coolant were sampled from the reactor dump tank for off-line radiochemical analysis. The18F was separated as trimethylfluorosilane and the activity was determined by measurement of the 0.511 MeV annihilation photopeak using a NaI(TI) detector. The measured18F activity was used to determine actual in-core reactor power using both ab-initio calculations and by comparison of results with a calibrated power reactor. The18F data also provided a method of nomalising the16N data for direct monitoring of in-core reactor power in JASON. 相似文献
998.
The compositional dependence of the glass transition temperature (T g), and the temperature of the maximum rate of crystallization (T p) of As-Se glasses containing Sb has been measured using non-isothermal DSC. The variation of these characteristic temperatures is found useful in interpreting the structural changes in As-Sb-Se glasses. The role of Sb in these glasses and its effect on the crystallization characteristics is analyzed. 相似文献
999.
THE EFFECTS OF PORPHYRIN STRUCTURE AND AGGREGATION STATE ON PHOTOSENSITIZED PROCESSES IN AQUEOUS AND MICELLAR MEDIA 总被引:2,自引:0,他引:2
C. R. Lambert E. Reddi J. D. Spikes M. A. J. Rodgers G. Jori 《Photochemistry and photobiology》1986,44(5):595-601
The efficiency of several porphyrins at 10 μM and 83 μM as sensitizers of the photooxidation of 0.1 mM tryptophan and histidine via a singlet oxygen-mechanism was studied in pH 7.4-buffered aqueous solutions and in aqueous dispersions of Triton X-100 micelles. The porphyrins were either solubilized in the bulk aqueous medium or associated with the micellar phase, whereas the amino acids were always located in the aqueous phase. With those porphyrins, such as uroporphyrin I, meso-tetra (4-sulfonatophenyl)porphine, meso-tetra(4-carboxyphenyl)porphine and meso-tetra)N,N,N-trimethylanilinium)porphine, which are > 98% monomeric in both media, the efficiency of histidine photooxidation was independent of the site of O2(1Δg) generation, as shown by the closely similar values for the photooxidation rate constant and oxygen-consumption quantum yield in the presence and absence of Triton micelles; the same indications were provided by photokinetic experiments with tryptophan. Actually, laser flash photolysis studies showed that the micelle-incorporation of the above mentioned porphyrins brought about only minor changes in their photophysical properties, including the relative yield of O2(1Δg) generation. On the other hand, hematoporphyrin IX, its Zn2+-complex, and coproporphyrin III are largely aggregated in homogeneous aqueous solution; their incorporation into Triton micelles caused an increase of the triplet quantum yield and an enhancement of the oxygen-consumption quantum yield and photooxidation rate constant for both histidine and tryptophan. The lower photosensitizing efficiency of aggregated porphyrin species in comparison with the corresponding monomeric porphyrin was confirmed by measuring the initial rate and quantum yield of oxygen consumption upon irradiation of 1 mM histidine and tryptophan in the presence of different hematoporphyrin concentrations within the 0.3-100μM range. 相似文献
1000.
C. Wasilevsky M. de la Vega Vedoya S. J. Nassiff 《Journal of Radioanalytical and Nuclear Chemistry》1985,89(2):531-543
Excitation functions have been measured for yields of In isotopes in the reactions107Ag(, xn)111–xIn and109Ag(, xn)113–xIn for x=1–5. The alpha particle bombardment of natural silver, the stacked foil technique for irradiation and semiconductor gamma-spectrometry for measurements were used.This work has been sponsored by the Subsecretaría de Ciencia y Tecnología, Argentina. 相似文献