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11.
trans-Pd(NO3)H(PCy3)2 (I) when treated with Et4NCl forms the hydride trans-PdClH(PCy3)2 which in turn reacts with AgPF6 in acetonitrile to give trans-[PdH(CH3CN)(PCy3)2]PF6 (III). Both I and III react smoothly with acetylenes containing one electron-withdrawing group to give alkenyl products. The geometry of the resulting alkenyl ligand implies that cis addition has occurred and that the hydridic hydrogen adds to the acetylenic carbon containing the electron-withdrawing group.Acetylenes containing two electron-withdrawing groups give mixtures from which both alkenyl and zerovalent acetylene compounds can sometimes be isolated. In the presence of proton sponge, monosubstituted acetylenes still give alkenyl products while those substituted with two electron-withdrawing groups give the zerovalent products in good yield. The relevance of these results to an understanding of the nature of the migratory insertion reaction is discussed. 相似文献
12.
The reactions of Fe(CO)5, Fe(CO)4P(C6H5)3, M(CO)6 (M W, Mo, Cr), and (CH3C5H4Mn(CO)3 with KH and several boron and aluminium hydrides were investigated. Iron pentacarbonyl was converted quantitatively to K+Fe(CO)4-(CHO) by hydride transfer from KBH(OCH3)3 allowing isolation of [P(C6H5)3]2-Nn+Fe(CO)4(CHO)? in 50% yield. Lower yields were obtained with LiBH(C2H5)3, and other hydride sources gave little or no formyl product. The stability of Fe(CO)4(CHO)? in THP was found to depend on the cation, decreasing in the order [P(C6H5)3]2N+ > K+ > Na+ > Li+. No formyl complexes were isolated and no spectroscopic evidence for formyl formation was observed in the reactions of the other transition metal carbonyls with several hydride sources. Fe(CO)4-P(C6H5)3 gave K2Fe(CO)4 when treated with KHB(OCH3)3. When treated with LiBH(C2H5)3, W(CO)6 gave a mixture of HW2(CO)10?and (OC)5W(COC2H5)?; the latter was methylated to give the carbene complex (OC)5WC(OCH3)C2H5. 相似文献
13.
The proton NMR spectra of N-[2-pyridyl-N-oxide]-derivatives of primary and secondary ethylamines, containing a substituent R on the C atom bearing the amino function, have been completely analysed in terms of the fundamental NMR parameters. The preferred conformations of the compounds investigated were established by the indications from NOE experiments as well as: (1) the long range coupling across the five bond between the aminic hydrogen and the proton in 4-position of the pyridine-N-oxide ring (5JmH,NH ~ 0·5 c/s), (2) the value of the vicinal coupling constant in the fragment CHNH (3JNHCH ~ 7–9 c/s), (3) the large deshielding (Δτ ~ 1–1·5 ppm) observed for the resonance position of the proton on the asymmetric C atom in secondary amine derivatives with respect to the corresponding primary ones, and (4) the diamagnetic shielding produced on protons in position 3 and 4 of the pyridine-N-oxide ring by different aromatic groups introduced in the R substituent.The NMR data confirmed the preferred rotamers previously suggested on the basis of ORD and CD measurements. 相似文献
14.
ZHOU Hai-cheng XU Sheng PENG Qing LI Ya-dong 《高等学校化学研究》2006,22(1):11-13
IntroductionNano-sized semiconductors are of great interestdue to their special optical and electronic proper-ties[1,2].As one of the mostimportantⅡ—Ⅵsemicon-ductors,CdS has importantapplications in many fields,such as the solar cell field,non linear o… 相似文献
15.
J. Krempaský 《Journal of Non》1978,27(1):135-137
On the basis of the agreement of calculated and measured parameters of some amorphous semiconductors, an argument is stated in favour of the central-symmetric type of random local electric fields. A possible mechanism of the transport of electrons is discussed. 相似文献
16.
《Current Applied Physics》2015,15(7):805-810
The acoustic and thermal properties of the liquid–glass transitions of propylene glycol and its oligomers, poly (propylene glycol)s, were studied by temperature modulated DSC and Brillouin scattering. The fragility indices were determined from Angell plots using the observed modulation frequency dependence of the complex heat capacity. The variation in the glass transition temperatures is discussed on the basis of the free volume theory. The relaxation time of the structural relaxation obeys the Vogel–Fulcher law, and its high frequency end is in good agreement with the result of the dielectric measurement in the literature. The correlation between the observed thermal expansion coefficients and the glass transition temperature is discussed based on the free volume theory. The sound velocity and attenuation were accurately determined as a function of the temperature by Brillouin scattering by combination with the refractive index measurement. The relaxation dynamics were discussed by considering the relaxation from segmental motions. All of these physical properties were discussed based on the third-order anharmonicity and the Grüneisen parameter. 相似文献
17.
三维频域自由面格林函数及其偏导数的数值计算是海洋结构物水动力分析的难点.本文对有限水深格林函数及其偏导数的数值算法作出两点改进:①对原函数的级数表达式进行变形,提出适用于数值计算的形式,解决高频率情况下级数解的计算失真问题;②对Gauss-Laguerre积分法作出改进,解决高频率大水深情况下积分解的数值溢出问题.计算... 相似文献
18.
19.
根据单个保单理赔额分布函数F(z)的一些特殊性质,研究了开放个别风险模型在保单个数N为Poisson分布下,总理赔额分布函数F_S(x)对任意x(x≥0)的界值问题,得到一些实用的、便于数值计算的界值结果,具有重要的应用价值. 相似文献
20.
Gap opening and tuning in single-layer graphene with combined electric and magnetic field modulation 下载免费PDF全文
The energy band structure of single-layer graphene under one-dimensional electric and magnetic field modulation is theoretically investigated. The criterion for bandgap opening at the Dirac point is analytically derived with a two-fold degeneracy second-order perturbation method. It is shown that a direct or an indirect bandgap semiconductor could be realized in a single-layer graphene under some specific configurations of the electric and magnetic field arrangement. Due to the bandgap generated in the single-layer graphene,the Klein tunneling observed in pristine graphene is completely suppressed. 相似文献