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61.
Three hydrogen bonding complexes of the gauche‐1PA dimer (GG), trans‐1PA dimer (TT) and mixed dimer (GT) have been calculated for the geometry conformations and excited‐state energies. The electron distribution at the site of C‐O of H‐donor moiety in HOMO transfers to the direction of O‐H of H‐acceptor moiety in LUMO. The hydrogen bond between two 1PAs is the bridge of the intermolecular charge transfer. By the Zhao and Han's excited‐state hydrogen bonding dynamics rule, the first excited‐state hydrogen bonding change has been discussed without optimizing the excited‐state geometry conformations. According to the distinct difference between GT and GG (TT), we concluded that two gauche‐1PA monomers of one dimer are transformed at the same time to two trans‐1PA monomers. 相似文献
62.
Jaewoong Kim 《Linear and Multilinear Algebra》2017,65(6):1260-1275
In this paper, we study several properties for mono-weakly hyponormal 2-variable weighted shifts. First, we consider propagation phenomena for mono-weakly hyponormal (resp. mono-polynomially hyponormal) 2-variable weighted shifts. Next, we contemplate the mono-weak hyponormality under the Schur product. Finally, we study whether the mono-weak hyponormality is invariant under powers. 相似文献
63.
We study the Goos-Hänchen (GH) shifts for Dirac fermions in graphene scattered by a triangular double barrier potential. The massless Dirac-like equation was used to describe the scattered fermions by such potential configuration. Our results show that the GH shifts is affected by the geometrical structure of the double barrier. In particular the GH shifts change sign at the transmission zero energies and exhibit enhanced peaks at each bound state associated with the double barrier when the incident angle is less than the critical angle associated with total reflection. 相似文献
64.
Normal halogen dependence of 13C NMR chemical shifts of halogenomethanes revisited at the four‐component relativistic level
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Dmitry O. Samultsev Yury Yu. Rusakov Leonid B. Krivdin 《Magnetic resonance in chemistry : MRC》2016,54(10):787-792
The ‘Normal Halogen Dependence’ of 13C NMR chemical shifts in the series of halogenomethanes is revisited at the four‐component relativistic level. Calculations of 13C NMR chemical shifts of 70 halogenomethanes have been carried out at the density functional theory (DFT) and MP2 levels with taking into account relativistic effects using the four‐component relativistic theory of Dirac‐Coulomb within the different computational methods (4RPA, 4OPW91) and hybrid computational schemes (MP2 + 4RPA, MP2 + 4OPW91). The most efficient computational protocols are derived for practical purposes. Relativistic shielding effect reaches as much as several hundreds of ppm for heavy halogenomethanes, and to account for this effect in comparison with experiment at the qualitative level, relativistic Dyall's basis sets of triple‐zeta quality or higher are to be used within the framework of the four‐component relativistic theory taking into account solvent effects. Relativistic geometrical optimization (as compared with the non‐relativistic level) is essential for the molecules containing at least two iodines at one carbon atom. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
65.
Roy E. Hoffman Noach Treitel Mordecai Rabinovitz 《Magnetic resonance in chemistry : MRC》2001,39(8):489-494
Isotope shifts are a well-established tool for structural analysis by NMR. The substitution of a protium with a deuterium is the most widely studied of these effects. However, such studies call for specific deuteration that requires complex synthetic techniques owing to the low natural abundance of deuterium. 13C occurs at a higher natural abundance and couples strongly with its attached proton. We have developed and refined a method to reliably observe these much smaller shifts without needing to resort to chemical synthesis. We show that carbon induced isotope shifts reflect structural features. Copyright © 2001 John Wiley & Sons, Ltd. 相似文献
66.
采用单组态坐标模型,应用由对角化d3能量矩阵而获得的波函数,同时考虑了自旋-轨道相互作用和电-声子耦合,并定量计入了4T2与2T1各电子态对R线的影响以及局域压缩率和整体压缩率之间的差异,从微观的角度,研究了GSGG∶Cr3+低温下光谱结构的特点以及压力导致的R1线和4T2宽带的移位.理论计算的结果与实验符合较好,R线的常压位置及其分裂、R1线的压致移位及其"反转"现象和4T2宽带的压致移位都得到了合理的解释. 相似文献
67.
Ch. Lisdat N. Vanhaecke D. Comparat P. Pillet 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2002,21(3):299-309
Two-photon photoassociation spectra in a Λ-type excitation scheme are analysed under the systematically varied experimental conditions of frequency detunings and laser
intensities. Line shape fits are presented as well as the investigation of intensity and detuning dependent line shifts. From
both we determine the attained spectroscopic precision, that is corrected for a systematic line shift due to the thermal distribution
of atoms in the trap. An energy correction for this effect is given. Information about the feasibility of generating translationally
cold molecules in a well defined rotational and vibrational level by the photoassociation process is derived from the analysis.
Received 21 May 2002 Published online 15 October 2002
RID="a"
ID="a"Current address e-mail: christian.lisdat@ptb.de
RID="b"
ID="b"e-mail: pierre.pillet@lac.u-psud.fr 相似文献
68.
Recent measurements revealed that commercial magnesium standard solutions showed isotopic abundance variations, which cannot clearly be distinguished from each other by calibrating against the only available isotopic reference material, SRM 980, or reference materials made from SRM 980 like IRMM-009. Therefore new SI-traceable magnesium isotopic reference materials are required. 相似文献
69.
It is shown that the class of perturbations of the semigroup of shifts on by unitary cocycles with the property (where is the Hilbert-Schmidt class) contains strongly continuous semigroups of isometric operators, whose unitary parts possess spectral decompositions with the measure being singular with respect to the Lebesgue measure. Thus, we describe also the subclass of strongly continuous groups of unitary operators that are perturbations of the group of shifts on by Markovian cocycles with the property .
70.
We describe a new experiment for measuring homonuclear-decoupled anisotropic chemical shift patterns in doubly 13C-labeled compounds under magic-angle spinning. The experiment combines a pair of selective and non-selective 180 degrees pulses to suppress the 13C-13C scalar and dipolar interactions. This is combined with the recently developed SUPER technique to recouple the chemical shift anisotropy. Demonstrations on 13Calpha and 13CO-labeled amino acids and peptides show that accurate chemical shift powder patterns can be obtained. This permits the use of chemical shift anisotropy for conformational studies of suitably extensively 13C-labeled peptides and proteins. 相似文献