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21.
INTRODUCTION The tensor associated with a Raman band plays an important role in determining the band intensity and its structural significance. Each Raman tensor interrelates two electric vectors, that of the exciting radiation (i.e. laser photon) and that of the Raman scattered radiation (i.e. the inelastically scattered photon which results from the exchange of a vibrational quantum between the exciting photon and the molecule). The Raman tensor is obtained formally as the first derivative of the molecular polarizability tensor, the derivative being taken with respect to the vibrational normal coordinate. In other words, the Raman tensor associated with a vibrational Raman band is an indicator of how the polarizability of the molecule oscillates with the molecular normal mode of vibration. 相似文献
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Recent research has shown that a phase transformation of diamond to a different form of carbon is involved when diamonds are polished in the traditional fashion. The question as to how this phase transformation is activated and maintained to produce high wear rates is of great technological interest since it may radically change the way we view the processing of diamond. This paper describes the use of Raman spectroscopy to examine debris produced on the diamond polishing wheel, both during its preparation and during polishing. In addition, polished diamond surfaces were examined for the possible existence of non-diamond surface layers in an attempt to identify material removal mechanisms. Raman spectroscopy proves ideal for these analyses because its relatively high spatial resolution is well suited to the analysis of small wear features and debris particles, and because of the wealth of information it reveals about chemical structure. This level of structural information has been lacking in previous analyses of diamond polishing debris. In addition to the non-diamond carbon found in the wear debris, significant quantities of two iron oxides, magnetite (Fe3O4) and haematite (α-Fe2O3), were also found. An interesting observation was that a transformation from magnetite to haematite could be induced either by using high power laser excitation or by frictional heating during polishing. It is suggested that some of the Raman peaks previously attributed to lonsdaleite might better be explained by the presence of these oxides. 相似文献
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The potential energy curves of the rare gas dimers He2, Ne2, and Ar2 have been computed using correlation consistent basis sets ranging from singly augmented aug-cc-pVDZ sets through triply augmented t-aug-cc-pV6Z sets, with the augmented sextuple basis sets being reported herein. Several methods for including electron correlation were investigated, namely Møller—Plesset perturbation theory (MP2, MP3 and MP4) and coupled cluster theory [CCSD and CCSD(T)]. For He2 CCSD(T)/d-aug-cc-pV6Z calculations yield a well depth of 7.35 cm-1 (10.58 K), with an estimated complete basis set (CBS) limit of 7.40 cm-1 (10.65 K). The latter is smaller than the 'exact' well depth (Aziz, R. A., Janzen, A. R., and Moldover, M. R., 1995, Phys. Rev. Lett., 74, 1586) by about 0.2 cm-1 (0.35 K). The Ne2 well depth, computed with the CCSD(T)/d-aug-cc-pV6Z method, is 28.31 cm-1 and the estimated CBS limit is 28.4 cm-1, approximately 1 cm-1 smaller than the empirical potential of Aziz, R. A., and Slaman, M., J., 1989, Chem. Phys., 130, 187. Inclusion of core and core—valence correlation effects has a negligible effect on the Ne2 well depth, decreasing it by only 0.04 cm-1. For Ar2, CCSD(T)/d-aug-cc-pV6Z calculations yield a well depth of 96.2 cm-1. The corresponding HFDID potential of Aziz, R. A., 1993, J. chem. Phys., 99, 4518 predicts of De of 99.7 cm-1. Inclusion of core and core-valence effects in Ar2 increases the well depth and decreases the discrepancy by approximately 1 cm-1. 相似文献
24.
William S. Port John E. Hansen E. F. Jordan JR. T. J. Dietz Daniel Swern 《Journal of polymer science. Part A, Polymer chemistry》1951,7(2-3):207-220
Contrary to some published reports, the vinyl esters of saturated fatty acids polymerize readily and rapidly. Vinyl oleate, when present in excess of 5%, and oxygen exert marked retarding effects. Techniques are described for the free-radical-initiated polymerization of the vinyl esters of caprylic, capric, lauric, myristic, palmitic, and stearic acids in bulk, dispersion, solution, and emulsion. Some data are given for polymerization in the presence of chain-transfer agents, such as carbon tetrachloride, dodecylmercaptan, and ethylbenzene. Conditions are reported for obtaining degrees of polymerization from about 2 (when chain-transfer agents are employed) to 10,000 (weight average). The weight average degree of polymerization increases markedly as the conversion increases, particularly above 80%. Even up to extremely high conversions, soluble polymers are obtained in most cases. Solubility characteristics, transition point data, molecular weights (osmometric and light-scattering), and isolation and purification techniques are also reported. 相似文献
25.
Hexabromocyclododecane (HBCD) is a flame retardant that is undergoing environmental risk assessment. The liquid chromatographic retention and electrospray ionization matrix effects were investigated for HBCD methods of analysis for environmental matrices. Column selectivity towards HBCD diastereomers was evaluated for C30 and C18 stationary phases under different mobile phase conditions and column temperatures. The HBCD elution order was dependent on the shape selectivity of the stationary phase and the mobile phase composition. Greater resolution, on columns with reduced shape selectivity, of beta-HBCD and gamma-HBCD was achieved with the use of an acetonitrile/water (compared with a methanol/water) mobile phase composition. A liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) method for the analysis of HBCD in biological tissues was evaluated for potential matrix effects. The influence of extracted matrix components on HBCD diastereomer and enantiomer analysis was investigated using a postextraction addition approach. Although the analysis of HBCD diastereomers was relatively unaffected by the sample matrix, the responses of the HBCD enantiomers in tissue samples were significantly influenced by matrix effects and other changes to the ionization conditions. The use of racemic 13C-labeled HBCD diastereomers as internal standards for enantiomer fraction measurements corrected for the changes in the mass spectrometer response. 相似文献
26.
本文报导了采用氩离子激光器来泵浦Pr3+:YLF晶体,应用声光调制器实现了主动锁模;同时应用振动─高反射平面镜也实现了被动锁模,两种锁模均得到了ps光脉冲.据作者了解这是这种晶体材料的第一次锁模运转. 相似文献
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THE AVAILABILITY OF SOLAR RADIATION BELOW 290 nm AND ITS IMPORTANCE IN PHOTOMODIFICATION OF POLYMERS
R. E. BARKER JR. 《Photochemistry and photobiology》1968,7(3):275-295
Abstract— On a percentage basis, ozone is a very minor component of the atmosphere; at STP it would make a layer only about 2 mm thick. On almost every other basis (biological, meteorological, paleontological, photochemical, etc.) it is a major component, due mainly to the tremendous reduction in solar ultraviolet flux which it causes in the 220–290 nm region. Since no data are available for Λ < 285 nm, a rational basis for estimating the flux reaching the earth's surface in this region is discussed. Variations in ozone concentration are of great importance, and it is possible to have more radiation with Λ < 270 nm fall on a surface in one extreme day than in several years of typical days. Often, persons involved in studies of polymer degradation by sunlight mention that a negligible fraction (1 ppm) of the radiant flux reaching the earth's surface is associated with wavelengths below 290 nm and infer that studies at shorter wavelengths will not be of much practical value. Such inferences are questionable for at least two reasons. (1) The quantum flux density below 290 nm is about 1016 photons cm-2 month-1 , so that considerable long-term damage is possible since most of the flux will be absorbed in a layer only a few microns thick. (2) Even if solar radiation below 290 nm were completely absent, the existence of correlations between absorption peaks in the near ultraviolet and visible, and in the infrared with ionization potentials typically 6–12 eV or 200-100 nm) is evidence that we may expect studies in the ultraviolet and extreme ultraviolet (EUV) to provide important clues to the problem of improving the resistance of polymers to sunlight. 相似文献