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91.
A non-empirical molecular orbital method, particularly suitable for calculations on cage-like molecules, is described. The method uses as basis functions the set of free-electron functions which are the solutions of Schrödinger's equation for an electron confined between two concentric, spherical potential energy barriers. Application of the theory to the SCF calculation of the energies of the delocalized electrons in benzene and tetrasulphur tetranitride shows that the model is capable of interpreting the properties of such systems. However, it does highlight a difficulty in the calculation of excited state energies with one-centre models which appears to be largely unrecognized.Extension of the method to a consideration of all the valence electrons, using P4 as an example, reveals problems the origin of which is an inadequate treatment of the core electrons. It is suggested that these problems may best be dealt with by use of a suitable pseudo potential. 相似文献
92.
《Electroanalysis》2004,16(8):650-655
An analytical solution is developed for heterogeneous ECE processes occurring at channel electrode surface for both laminar and turbulent flow. The solution explicitly links the behavior of ECE processes and the parameters. A simple expression of the effective number of electrons transferred, covering all the reaction rate constants and different diffusion coefficients of the reactant A and the intermediate product B, is obtained. Excellent agreement with previous numerical and analytical results is shown . Parametric studies illustrate the effects of diffusion coefficients, hydrodynamic factors and reaction rate constants on the effective number of electrons transferred and the currents. 相似文献
93.
L.A. Leites A.V. Zabula S.S. Bukalov A.A. Korlyukov P.S. Koroteev O.S. Maslennikova M.P. Egorov O.M. Nefedov 《Journal of Molecular Structure》2005,750(1-3):116-122
Vibrational (Raman and IR) spectra of the 1:1 complexes of dihalogermylene and dihalostannylene with 1,4-dioxane and PPh3 have been reported, the structures of the complexes Cl2Ge·C4H8O2 and Cl2Ge·PPh3 updated using high-resolution X-ray method. Quantum-chemistry calculations of the geometry and normal mode frequencies and eigenvectors were carried out for some of the complexes. The results show that in the structure of the polymeric solid complexes of X2M with 1,4-dioxane, intermolecular coordination XM plays a prominent role, whereas the corresponding complexes with PPh3 are monomeric. In the vibrational spectra of all the complexes, an inversion of symmetric and antisymmetric stretching νXM (X=Cl, Br; M=Ge, Sn) frequencies, found for ‘free’ X2MII particles, still persists, suggesting that the X2M moieties preserve their specifity as carbene analogues also in the complexes. 相似文献
94.
As an extension of previous reports, the barium carbonate procedure has been optimized in detail for the preparation of apolar columns. The aim was to produce optimum overall column characteristics, and to maintain them unchanged under the prolonged influence of the highest possible temperature. The main parameters under optimization were glass variety, leaching of glass surface with aqueous HCl, and amount of barium carbonate deposited, while deactivation and coating were kept constant. The basic column characteristics were adsorption properties and thermostability of deactivation, acid/base behaviour and separation efficiency. They were determined by a new, quantitative testing procedure. Intense leaching was able to eliminate almost totally the differences between glass varieties and to create a well-defined glass surface. While untreated glass, leached glass, and barium carbonate treated glass showed specific weak points in the respective column quality, the combination of leaching and barium carbonate treatment yielded the highest and most stable quality. Some technical modifications of the preparation procedure are described, including deactivation in the gas phase, and use of pentane as a solvent for static coating. 相似文献
95.
Ingemar Wadsö 《Thermochimica Acta》1985,96(2):313-325
The field of isothermal microcalorimetry as applied to systems of interest for aqueous solution chemistry, biochemistry and in cellular biology is briefly reviewed. Some techniques recently developed in the author's laboratory are described. 相似文献
96.
探针反应和FTIR法研究Pt与L型沸石的相互作用董家禄,朱建华,须沁华,张婕,刘大壮(南京大学化学系,南京,210008)(郑州工学院化工系,郑州,450002)关键词Pt/L沸石,沸石催化剂,异丙醇分解反应,Pt-载体相互作用Pt的分散度和电子状态... 相似文献
97.
Immobilized sulfhydryl groups were prepared by partial thiolation of NH2-glass beads. The microenvironment of the immobilized SH groups was varied by different chemical modifications of neighboring
NH2 groups. Introduction of a strong charge in the surroundings of immobilized sulfhydryls results in their dramatic stabilization
against autooxidation. This effect is due to the salting of O2 from the surface microlayer of the thiolated beads. 相似文献
98.
Marti E. Kaisersberger E. Emmerich W.-D. 《Journal of Thermal Analysis and Calorimetry》2004,77(3):905-934
The definitions of the temperature resolution, the so-called resolution of DSC instruments given in literature are discussed.
A new definition of the resolution for DSC instruments is presented and outlined. The main characteristic introduced in this
new definition is a minimum between two caloric events as a prerequisite of an existing resolution. Possible candidates of
test substances have been evaluated. The oligomer n-hexatriacontane is revealing an interesting phenomenon, namely a lambda
transition which is in the peak temperature only 2 K lower than the melting temperature of 76°C. The substance was selected
as an ideal test substance for the quantification of the resolution of DSC instruments. The lambda transition is a second
order process which may reach under certain conditions the saturation of the occurring molecular dislocation within 0.2 K,
and after saturation the heat flow rate drops sharply down. Investigations concerning the main characteristics of n-hexatriacontane
in respect to the temperatures of transition (lambda transition and melting), to the involved enthalpies, and to the resolution
factors were performed as functions of the sample mass and the heating rate. The importance of relevant evaluation procedures
increasing the resolution factors of DSC curves are discussed and these procedures are integrated into the testing of the
resolution. The necessity for widening the experimental scope from instruments to evaluation procedures is forced by the existence
of instruments with built-in signal treatments based on electronic devices and software procedures. A comparison with literature
data is outlined for all of the mentioned characteristic values of n-hexatriacontane.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
99.
Petr Niederhafner 《Tetrahedron letters》2006,47(6):1023-1025
Peptides from the hinge region of human IgG1 are potential defined carriers of synthetic immunogens. Their synthesis was carried out on the soluble support—PEG-OMe 2000 using disulfide bond synthons. The loading capacity of the polymer was increased twofold by anchoring the lysine as a simple branching unit. The amino acid leucine was used as an enzymatically cleavable linker. Peptide detachment from the polymer was performed either by classical ester bond saponification or newly by peptide bond cleavage catalyzed by thermolysin in water. 相似文献
100.
The title compound, Cu(S2CNEt2)2, behaves at low temperatures (1–20 K) as a normal spin-1/2 molecule, with 〈g〉 =2.06 and the Curie-Weiss θ = +0.25 K. This result contradicts an earlier investigation that led to the suggestion that the crystallographically-occurring dimers are coupled ferromagnetically. 相似文献