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1.
We demonstrate that the crystallization of thin, supported amorphous solid water layers is initiated at the water surface. This is concluded from the observation of sequential crystallization of amorphous water at the surface, in the bulk, and at the water-support interface. A surface nucleation model quantitatively reproduces the observed transformation kinetics at the three sites.  相似文献   
2.
Laser-induced desorption of water molecules from nanometer amorphous solid water films supported on a single-crystal platinum substrate is reported. A femtosecond laser pulse creates hot substrate electrons, which are injected into the water layer, resulting in significant desorption at the water-vacuum interface. The dependence of the desorption yield on film thickness and results for isotopic spacer and capping layers reveal that the desorbing water originates from relatively deep down into the water layer, i.e., from several nanometers below the surface. This is proposed to be the result of cooperative electronic effects resulting from the high electron densities in the thin water film, which cause a transient destabilization of the water H-bonded network. Motion of excited water molecules through the layer is enabled by mixing within the layer on ultrafast timescales during the desorption process.  相似文献   
3.
Fast atom bombardment, combined with high-energy collision-induced tandem mass spectrometry, has been used to investigate gas-phase metal-ion interactions with captopril, enalaprilat and lisinopril, all angiotensin-converting enzyme inhibitors.Suggestions for the location of metal-binding sites are presented. For captopril, metal binding occurs most likely at both the sulphur and the nitrogen atom. For enalaprilat and lisinopril, binding preferably occurs at the amine nitrogen. Copyright 1999 John Wiley & Sons, Ltd.  相似文献   
4.
If J is an analytic, saturated gambling house with compact sections, and we show that there exists a (submarkovian) borel kernel P permitted in J such that μ = λP. If is a proper submarkovian resolvent on a Lusin space X, we study the regularity of the reduite RAs of an excesive function s on a set AX.  相似文献   
5.
Electrospray mass spectrometry/mass spectrometry was used to investigate the gas‐phase properties of protonated expanded porphyrins, in order to correlate those with their structure and conformation. We have selected five expanded meso‐pentafluorophenyl porphyrins, respectively, a pair of oxidized/reduced fused pentaphyrins (22 and 24 π electrons), a pair of oxidized/reduced regular hexaphyrins (26 and 28 π electrons) and a regular doubly N‐fused hexaphyrin (28 π electrons). The gas‐phase behavior of the protonated species of oxidized and reduced expanded porphyrins is different. The oxidized species (aromatic Hückel systems) fragment more extensively, mainly by the loss of two HF molecules. The reduced species (Möbius aromatic or Möbius‐like aromatic systems) fragment less than their oxidized counterparts because of their increased flexibility. The protonated regular doubly fused hexaphyrin (non‐aromatic Hückel system) shows the least fragmentation even at higher collision energies. In general, cyclization through losses of HF molecules decreases from the aromatic Hückel systems to Möbius aromatic or Möbius‐like aromatic systems to non‐aromatic Hückel systems and is related to an increase in conformational distortion. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   
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7.
For a submarkovian resolvent U=(U )>0 with bounded initial kernel U 0 on a Radon space X, we construct a minstable cone of potentials C on a compact metrizable space YX such that U extends to a subordonated (to C) resolvent on Y.  相似文献   
8.
We present an experimental and theoretical investigation of the adsorption, desorption, and dissociation of NO on the stepped Pt (533) surface. By combining temperature programmed desorption and reflection absorption infrared spectroscopy, information about the adsorption sites at different temperatures is obtained. Surprisingly, metastable adsorption structures of NO can be produced through variation of the dosing temperature. We also show that part of the NO molecules adsorbed on the step sites dissociates around 450 K. After dissociation the N atoms can desorb either by combining with an O fragment, or with another N atom, resulting in NO and N(2). The N(2) production can be enhanced by coadsorbing CO on the surface: CO scavenges the oxygen atom, thereby suppressing associative recombinative desorption of N and O atoms. Density functional theory calculations are used to reveal the adsorption energies and vibrational frequencies of adsorbed NO as well as barriers for dissociation of NO and for diffusion of N atoms. The combined experimental results and theoretical calculations reveal that dissociation of NO is the rate limiting step in the formation of N(2).  相似文献   
9.
Given the (canonical) Markov process associated with a sufficiently general semigroup (P t ), we establish a result concerning the uniform completeness of a family of L 2-spaces naturally associated with the jumps of the process. An application of this result is presented.  相似文献   
10.
Using a novel differential magneto-optical imaging technique we investigate the phenomenon of vortex lattice melting in crystals of Bi2Sr2CaCu2O8 (BSCCO). The images of melting reveal complex patterns in the formation and evolution of the vortex solid-liquid interface with varying field (H)/temperature (T). We believe that the complex melting patterns are due to a random distribution of material disorder/inhomogeneities across the sample, which create fluctuations in the local melting temperature or field value. To study the fluctuations in the local melting temperature/field, we have constructed maps of the melting landscape T m(H, r), viz., the melting temperature (T m) at a given location (r) in the sample at a given field (H). A study of these melting landscapes reveals an unexpected feature: the melting landscape is not fixed, but changes rather dramatically with varying field and temperature along the melting line. It is concluded that the changes in both the scale and shape of the landscape result from the competing contributions of different types of quenched disorder which have opposite effects on the local melting transition.  相似文献   
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