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821.
Heiko Dartsch Christian Tessarek Timo Aschenbrenner Stephan Figge Carsten Kruse Marco Schowalter Andreas Rosenauer Detlef Hommel 《Journal of Crystal Growth》2011,320(1):108-112
Thermodynamic analyses of halide vapor phase epitaxy (HVPE) for the growth of ZnO were conducted to investigate the effects of growth conditions against growth rates. The partial pressures of gaseous species in equilibrium with ZnO and the resultant driving force for ZnO deposition are calculated with respect to temperatures, input H2 pressures and input VI/II ratios. It has been revealed that the driving force is weakly dependent on the temperature and is still positive even at 1200 °C, while it greatly decreases at higher temperatures in the presence of H2. The driving force is also significantly influenced when the VI/II ratio is below 1000. The experimental growth rates substantially agree with the dispositions of the driving force expected from the thermodynamic analyses. 相似文献
822.
Heterogeneous bubble nucleation at surfaces has been notorious because of its irreproducibility. Here controlled multibubble surface cavitation is achieved by using a hydrophobic surface patterned with microcavities. The expansion of the nuclei in the microcavities is triggered by a fast lowering of the liquid pressure. The procedure allows us to control and fix the bubble distance within the bubble cluster. We observe a perfect quantitative reproducibility of the cavitation events where the inner bubbles in the two-dimensional cluster are shielded by the outer ones, reflected by their later expansion and their delayed collapse. Apart from the final bubble collapse phase (when jetting flows directed towards the cluster's center develop), the bubble dynamics can be quantitatively described by an extended Rayleigh-Plesset equation, taking pressure modification through the surrounding bubbles into account. 相似文献
823.
Bare vanadium-oxide and -hydroxide cluster cations (V(m)O(n)H(o)+, m = 2-4, n = 1-10, o = 0, 1) were generated by electrospray ionization in order to examine their intrinsic reactivity toward isomeric butenes and small alkanes using mass spectrometric techniques. Two of the major reactions described here concern the activation of C-H bonds of the alkene/alkane substrates resulting in the transfer of two hydrogen atoms and/or attachment of the dehydrogenated hydrocarbon to the cluster cations; these processes are classified as oxidative dehydrogenation (ODH) and dehydrogenation, respectively. For the dehydrogenation of butene, it evolved as a general trend that high-valent clusters prefer ODH resulting in the addition of two hydrogen atoms to the cluster concomitant with elimination of neutral butadiene, whereas low-valent clusters tend to add the diene with parallel loss of molecular hydrogen. Deuterium labeling experiments suggest the operation of a different reaction mechanism for V2O2(+) and V4O10(+) compared to the other cluster cations investigated, and these two cluster cations also are the only ones of the vanadium-oxide ions examined here that are able to dehydrogenate small alkanes. The kinetic isotope effects observed experimentally imply an electron transfer mechanism for the ion-molecule reactions of the alkanes with V4O10(+). 相似文献
824.
Meyer C Pascui O Reichert D Sander LC Wise SA Albert K 《Journal of separation science》2006,29(6):820-828
A polymer-based RP sorbent was prepared by immobilizing a poly(ethylene-co-acrylic acid) copolymer with an acid mass fraction of 5% on silica by using a 3-glycidoxypropyl linkage. 13C cross-polarization/magic angle spinning NMR spectroscopy of the sorbent, either in the dry state or suspended in the mobile phase, showed an increase in mobility at elevated temperatures. Alkyl chain segments with gauche conformations were more mobile than chain segments with trans conformations. The strength of the 13C-1H dipolar couplings in the alkyl chains was measured using the constant time dipolar and chemical shift pulse sequence, revealing less molecular motion for the trans conformation. Non-linear van't Hoff plots were observed for separations of shape-constrained solutes (such as geometric beta-carotene isomers and polycyclic aromatic hydrocarbons). At higher temperatures, the retention behavior was similar to that of monomeric C18 sorbents, whereas at ambient and lower temperatures, enhanced shape-selective properties were exhibited similar to those of polymeric C30 sorbents. 相似文献
825.
The figures of merit of a pulsed glow discharge time-of-flight mass spectrometer (GD-TOFMS) as a detector for gas chromatography
(GC) analysis were evaluated. The mass resolution for the GD-TOFMS was determined on FWHM in the high mass range (208Pb+) as high as 5,500. Precision of 400 subsequent analyses was calculated on 63Cu+ to be better than 1% RSD with no significant drift over the time of the analysis. Isotope precision based on the 63Cu+/65Cu+ ratio over 400 analyses was 1.5% RSD. The limits of detection for gaseous analytes (toluene in methanol as solvent) were
determined to be as low as several hundred ppb or several hundred pg absolute without using any pre-concentration technique.
Furthermore, the different GD source parameters like capillary distance, cathode–anode spacing, and GD source pressure with
regards to the accessible elemental, structural, and molecular information were evaluated. It was demonstrated that each of
these parameters has severe influence on the ratio of elemental, structural, and parent molecular information in chemical
speciation analysis. 相似文献
826.
Schröder D Schwarz H Milko P Roithová J 《The journal of physical chemistry. A》2006,110(27):8346-8353
The structures of C(7)H(9)(+) ions generated by protonation of toluene are investigated by means of gas-phase infrared spectroscopy in conjunction with labeling experiments and complementary mass spectrometric studies. In full consistency with previous studies, the unimolecular as well as the multiphoton-induced dissociation of mass-selected C(7)H(9)(+) ions lead to losses of molecular hydrogen and methane. Labeling data clearly imply the occurrence of skeletal rearrangements of protonated toluene to isomeric structures in the course of fragmentation. Complementary reactivity studies indicate, however, that the C(7)H(7)(+) ions generated upon dehydrogenation of C(7)H(9)(+) bear the benzylium structure, rather than that of the more stable tropylium ion. Combination of labeling data and extensive theoretical studies lead to a scheme for the fragmentation of protonated toluene, which can account for all experimental findings reasonably well. As far as infrared spectroscopy of gaseous ions is concerned, the present results confirm the structural predictions derived from theory and provide evidence for the existence of protonated cycloheptatriene but also pose some questions about the comparability of intensities in multiphoton dissociation and linear absorption spectra. 相似文献
827.
Trage C Diefenbach M Schröder D Schwarz H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(9):2454-2464
The influence of anionic and neutral ligands on the reactivity of cationic iron complexes towards methanol, ethanol, and iso- and n-propanol has been investigated by means of electrospray ionization (ESI) mass spectrometry, and in key questions the experimental results are supported by DFT calculations. The chemical processes taking place when FeCl2+ is coordinated to a variable number of alcohol molecules were investigated by collision experiments, as well as reactivity and labeling studies. The most abundant cations formed upon ESI of FeCl3/ROH mixtures can be described as consisting of a covalently bound FeCl2+ core, which is stabilized by neutral ROH ligands, for example, FeCl2(CH3OH)n+. Indications for a hydrogen-bonding mechanism of ligands in the second coordination sphere are given by the observation of the formally hypercoordinated ion FeCl2(CH3OH)5+ and interpretation of kinetic data for n=4. Further, deuterium labeling experiments disclose a number of hidden hydrogen transfers and imply that complexes with n=1 and 2 can exist in two tautomeric forms. Upon change of the alcohol ligand from methanol to ethanol and propanol, additional reaction pathways become accessible, among which metal-assisted dehydration of the respective alcohols by means of an ion/dipole mechanism is the most important. 相似文献
828.
829.
830.
The structures of mass selected silver cluster cations Ag19 +, Ag38 +, Ag55 +, Ag59 +, Ag75 +, and Ag79 + have been probed at a temperature of 100 K by trapped ion electron diffraction. The structure assignment is carried out by comparison of the experimental scattering intensity with theoretical scattering functions of calculated candidate structures obtained by density functional theory. For the cluster sizes studied the resulting experimental data are invariably best described by structures based on the icosahedral motif, while closed packed structures can be ruled out. 相似文献