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21.
Two recent experiments for adsorbed acrylonitrile on the Si(001) surface reported different adsorption structures at 110 and 300 K. We investigate the reaction of acrylonitrile on Si(001) by first-principles density-functional calculations. We find that the so-called [4+2] structure in which acrylonitrile resides between two dimer rows is not only thermodynamically favored over other structural models but also easily formed via a precursor where the N atom of acrylonitrile is attached to the down atom of the Si dimer. The additional initial-state theory calculation for the C 1s core levels of adsorbed acrylonitrile provides an interpretation for the observed low- and room-temperature adsorption configurations in terms of the precursor and [4+2] structures, respectively. 相似文献
22.
Marshall M. Siegel Keiko Tabei Frank Lambert Leonard Candela Bart Zoltan 《Journal of the American Society for Mass Spectrometry》1998,9(11):1196-1203
The atmospheric pressure ionization (API) source for a commercial mass spectrometer was modified to operate as a dual source in both the electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) techniques by simultaneously utilizing the electrospray probe and the corona discharge needle. A switching box was designed to operate in either manual or programmable modes to permit rapid switching between ionization techniques without changing sources, probes, or breaking vacuum. The source can be operated using the following ionization techniques: ESI only, APCI only, ESI/APCI simultaneously, and ESI/APCI alternatingly. The optimum operating conditions for these ionization techniques were similar to the manufacturer’s original specifications except that the APCI flow rate was lower (~50 µL/min versus 1000 µL/min) and externally heated nebulizing gas was found to be desirable. A four-component mixture, introduced by flow injection, was used to demonstrate the versatility of the dual ESI/APCI source. 相似文献
23.
Empirical solvent parameters of silica surfaces are determined by means of solvatochromic dyes, e.g., Cu(tmen) (acac)+ ClO
4
–
/B(C6H5)
4
–
, Fe(phen)2(CN)2, and Michlers Ketone dissolved in 1,2-dichloroethane or cyclohexane. The values obtained by UV/VIS-measurements are compared with both the polarity scales of Kamlet and Taft and with Gutmann's donor and acceptor numbers. Kamlet and Taft's -parameter (the hydrogen-bond donation capacity of a solvent) is determined independently by means of salicylideneaniline. The * of silica is determined using 5-N,N-dimethylamino-5-nitro-2,2-bithiophene and the complex of tetracyanoethylene with Michlers Ketone, respectively. Further on the reliabilities of the obtained Kamlet-Taft parameters , , and * are checked by comparism with experimental and calculated values of theE
T(30)-parameter of silica by means of multi-parameter regression analysis. The surface properties of silica are influenced mainly by HBD-properties (75%) and dipolarity/polarizability * (20%), but hardly by the HBA-properties (<5%). UV/VIS-measurements were carried out in a special equipment with glass fiber optics, A drawing of the apparatus is given. 相似文献
24.
K. -H. Speidel J. Cub U. Reuter F. Passek H. -J. Wollersheim N. Martin P. Egelhof H. Emling W. Henning R. S. Simon R. Schmidt H. -J. Simonis N. Gollwitzer 《Zeitschrift für Physik A Hadrons and Nuclei》1991,339(2):265-268
It is shown that transient magnetic fields in Gd-host for20Ne ions at a mean velocity of 12.5v0(v0=c/137), considerably beyond the Bohr velocity of 1s electrons of Ne ions (v1s=10v0), are dominated by the Fermi contact field of these electrons. The first excited 2+-state of2Ne was used as probe. The derived value for the mean degree of polarization p1s=0.32(13), is surprisingly large, though still consistent with values obtained at lower velocities. Present calculations of spin exchange cross sections severely underestimate the observed polarization at this high velocity.The authors are grateful to the operating staff of the UNILAC for providing excellent beam conditions. They also thank Dr. P. Maier-Komor for preparing the delicate targets. Support by the BMFT is acknowledged. 相似文献
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Krzysztof K. Zborowski Ibon Alkorta Jose Elguero Leonard M. Proniewicz 《Structural chemistry》2012,23(2):595-600
An extension of the harmonic oscillator model of aromaticity (HOMA) model to systems with carbon–boron bonds is presented. Model parameters were estimated using experimental and theoretical bond lengths. It is shown that both approaches produce very similar HOMA models. In the second part of the article, the aromaticity levels of several model compounds containing carbon–boron bonds are calculated using the previously obtained parameters. The results of these calculations are compared with those provided by other aromaticity indices. The aromaticity of boron-containing compounds is also compared with the aromaticity of analogous compounds containing carbon and nitrogen. 相似文献
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Sagis LM 《Physical review letters》2007,98(6):066105
The fluctuations of highly permeable interfaces, encountered in phase-separated biopolymer solutions, liposomes, polymersomes, or colloidosomes, are investigated. An expression for the power spectrum of the height correlation function is derived for a multicomponent system, incorporating the effects of mass transfer across the interface, using nonequilibrium thermodynamics. We also derive an expression for the relaxation time of the height correlation function, and calculate the relaxation time for a phase-separated gelatin-dextran-water system. Comparing our expression with the expression for an impermeable interface shows that mass transfer has a significant impact on the relaxation time of the interface. 相似文献