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41.
Accordingly, the observation of oxygen selectivity on Na-K-A would indicate that nitrogen has a greater steric hindrance at the window than does oxygen. Using single crystal X-ray diffraction (SCXD), it was confirmed that K at 8-member rings was relocated to 6-member rings and that the location of Na at 8-member rings became uncertain with calcination. It was also observed that Na-K-A was thermally more stable than Na-A. Using magic angle spin nuclear magnetic resonance (MAS-NMR), it was confirmed that Na at 8-member rings irreversibly changed location from a symmetric position to an asymmetric position with calcination.Using the atomic positions determined by SCXD, the mean square displacements (MSD) of oxygen and nitrogen inside the crystal of Na-A and Na-K-A were estimated by means of molecular dynamic simulation (MD). When temperature was decreased, the MSD of nitrogen was reduced to a greater extent than that of oxygen and the MSD of nitrogen inside Na-K-A was reduced by a greater margin than that inside Na-A.  相似文献   
42.
S-Methyl thiomethacrylate (methyl thiolmethacrylate, MTMA) was polymerized with a variety of anionic initiators such as n-BuLi, octylpotassium, PhMgBr, and Et2AlNPh2 in toluene and THF. Stereoregularity of the polymer (PMTMA) was determined from the 1H-NMR spectrum of poly(methyl methacrylate), which had been derived from PMTMA, because the α-methyl resonance in the 1H-NMR spectrum of PMTMA was not satisfactorily solved owing to the overlap of pentad signals. The 13C-NMR spectrum of PMTMA also showed the splitting due to pentad sequences. Stereoregularity of PMTMA was always low compared with that of poly(methyl methacrylate), which was prepared under the same reaction conditions. MTMA was much more reactive than methyl methacrylate and methacrylonitrile in the copolymerization with n-BuLi in toluene and in THF at ?78°C. The lower stereoregulation of the polymerization of MTMA and the higher reactivity of MTMA were mainly ascribed to the higher resonance effect of MTMA.  相似文献   
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To investigate the proton/deuteron geometrical isotope effect of positively and negatively charged water complexes, H5O2+ and H3O2-, we have carried out accurate ab initio path integral simulations considering the electron correlation effect. It has been found that the isotope effect on the hydrogen bond is different between these two species in that the oxygen separation becomes shorter in H5O2+ while longer in H3O2- by deuteron substitution. This behavior is ascribed to the change in the quantum effect of hydrogen bonds whether the shared hydrogen is on a single or double well potential surface.  相似文献   
45.
Sol-Gel Formation of ITO Thin Film from a Sol Including ITO Powder   总被引:1,自引:0,他引:1  
Recently, low temperature synthesis of ITO thin film of low resistivity is desired in the field of LCD (Liquid Crystalline Display) production. This paper describes the results of experiment to produce ITO thin film from a sol containing crystalline ITO particles and alkoxides of In and Sn. Crystallization temperature of ITO thin film obtained from the sol mixed with ITO powder was lower than that of ITO from the sol without ITO powder. Furthermore, the resistivity of the former ITO thin film was lower than that of the latter. It was assumed that these results were attributed to the promotion effect of ITO crystalline particles to crystalize the amorphous ITO gel at lower temperature. This low temperature crystallization effect plays an important role in enhancing the crystallinity and electric conductivity of ITO thin film from sol-gel process.  相似文献   
46.
Modification of sol-gel derived indium oxide thin films using ultraviolet lasers was investigated. Irradiation by an ArF excimer (6.4 eV) and the fourth harmonic generation of a Nd : YAG laser (4.7 eV) was found to be effective in crystallization with a loss of hydroxyl groups and a decrease in the sheet resistance of the sol-gel films. Transparent crystalline indium oxide films were successfully obtained by 6.4 eV laser irradiation at fluences below 20 mJ/(cm2·shot), whereas degradation of the films was induced by a relatively high-fluence beam.  相似文献   
47.
This paper reports the two-photon absorbing and orange-red fluorescence emitting properties of a series of new 2,1,3-benzothiadiazole (BTD)-based D-pi-A-pi-D-type and star-burst-type fluorescent dyes. In the D-pi-A-pi-D-type dyes 1-6, a central BTD core was connected with two terminal N,N-disubstituted amino groups via various pi-conjugated spacers. The star-burst-type dyes 8 and 10 have a three-branched structure composed of a central core (benzene core in 8 and triphenylamine core in 10) and three triphenylamine-containing BTD branches. All the BTD-based dyes displayed intense orange-red color fluorescence in a region of 550-689 nm, which was obtained by single-photon excitation with good fluorescent quantum yield up to 0.98 as well as by two-photon excitation. Large two-photon absorption (TPA) cross-sections (110-800 GM) of these BTD dyes were evaluated by open aperture Z-scan technique with a femtosecond Ti/sapphire laser. The TPA cross-sections of D-pi-A-pi-D-type dyes 2-6 with a benzene, thiophene, ethene, ethyne, and styrene moiety, respectively, as an additional pi-conjugated spacer are about 1.5-2.5 times larger than that of 1c with only a benzene spacer. The TPA cross-sections significantly increased in three-branched star-burst-type BTDs 8 (780 GM) with a benzene core and 10 (800 GM) with a triphenylamine core, which are about 3-5 times larger than those of the corresponding one-dimensional sub-units 9 (170 GM) and 11 (230 GM), respectively. The ratios of sigma/e(pi) between three-branched and one-dimensional dyes were 6.5:3.8 (for 8 and 9) and 6.0:4.0 (for 10 and 11), which are larger than those predicted simply on the basis of the chromophore number density (1:1), according to a cooperative enhancement of the two-photon absorbing nature in the three-branched system.  相似文献   
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Path-integral molecular dynamics simulations for the HCl(H2O)4 cluster have been performed on the ground-state potential energy surface directly obtained on-the-fly from semiempirical PM3-MAIS molecular orbital calculations. It is found that the HCl(H2O)4 cluster has structural rearrangement above the temperature of 300 K showing a liquid-like behavior. Quantum mechanical fluctuation of hydrogen nuclei plays a significant role in structural arrangement processes in this cluster.  相似文献   
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