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511.
Photolysis of [Mo(CN)8]4− in the presence of diethylenetriamine (dien) leads to the complexation of ligand via hydrogen in the stoichiometry 2:1. The mechanism of the complexation was investigated by spectroscopy absorption and the rate constants and the quantum yield determined. Rate constants and quantum yields for the formation of the final products were found to depend on pH, ligand, and metal cyanide concentration. The values are a maximum at pH 7.4. At pH >7.4 the reverse reaction, generating octacyanomolybdate complex from the heptacyano species, is faster. At low pH, the ligand is protonated and less reactive; hence, the rate of reaction and quantum yield values decrease. The ionic strength does not affect the reaction rate, implying an associative mechanism for the photochemical reaction with dien, supported by the rate law. The observed rate law is: © 1999 John Wiley & Sons, Inc. J Chem Kinet 31: 89–93, 1999 相似文献
512.
513.
Al Ansari S. V. Aksenova N. V. Popova T. V. 《Russian Journal of Coordination Chemistry》2001,27(3):172-174
Complexation in the Co(II)–H6X–H2O, Ni(II)–H6X–H2O, and Co(II)–Ni(II)–H6X–H2O systems (H6X is nitrilotrimethylenephosphonic acid) was studied by spectrophotometry. The formation of binuclear complexonates Ni2H2X · 7H2O, Co2H2X · 5H2O, and NiCoH2X · 6H2O was demonstrated. These compounds were isolated from the solution, their composition was determined, the thermal stability was studied, and the kinetic parameters of dehydration were calculated. 相似文献
514.
515.
Bulk and surface properties of the ionic liquids 1-alkyl-3-methyl-imidazolium iodides ([C(n)mim]I) were simulated by classical molecular dynamics using all atom non-polarizable force field (n = 4, butyl; 6, hexyl; 8, octyl). The structure of ionic liquids were initially optimized by density functional theory and atomic charges obtained by CHELPG method. Reduction of partial atomic charges (by 20% for simulation of density and surface tension, and by 10% for viscosity) found to improve the accuracy, while a non-polarizable force field was applied. Additionally, the simulation ensembles approach the equilibrium faster when the charge reduction is applied. By these refined force field parameters, simulated surface tensions in the range of 323-393 k are quite in agreement with the experiments. Simulation of temperature dependent surface tension of [C(4)mim]I well beyond room temperature (up to 700 K) permits prediction of the critical temperature in agreement with that predicted from experimental surface tension data. Simulated densities in the range of 298-450 K for the three ionic liquids are within 0.8% of the experimental data. Structural properties for [C(4)mim]I were found to be in agreement with the results of Car-Parrinello molecular dynamics simulation we performed, which indicates a rather well-structured cation-anion interaction and occurs essentially through the imidazolium ring cation. Diffusion coefficient changes with alkyl chain length in the order of [C(8)mim]I > [C(6)mim]I > [C(4)mim]I for the cation and the anion. Formation of a dense domain in subsurface region is quite evident, and progressively becomes denser as the alkyl chain length increases. Bivariate orientational analysis was used to determine the average orientation of molecule in ionic liquids surface, subsurface, and bulk regions. Dynamic bisector-wise and side-wise movement of the imodazolium ring cation in the surface region can be deduced from the bivariate maps. Atom-atom density profile and bivariate analysis indicate that the imidazolium cation takes a spoon like configuration in the surface region and the tilt of alkyl group is a function length of alkyl chain exposing as linear as possible to the vapor phase. 相似文献
516.
Proton magnetic relaxation rates of solutions of LiCl and LiI in isotopically labelled ethanols CH3CD3OD, CD3CH2OD and CD3CD2OH have been measured as functions of temperature and concentration mostly at v=30 MHz, where 21. The data were reduced in a way that revealed that CH3 and CH2 relaxation curves contained a residuum from the slow motion of the OH group in many cases. Thus, the rotational time correlation function of the CH3 and CH2 groups contain a residuum term stemming from the slow motion within the same molecule. The data show a threshold of the rotational energy which has to be exceeded in order to make the effect observable. 相似文献
517.
The expansion of the modified two-particle Ursell functionU(r) of a hardsphere quantal fluid is obtained in terms of a series of derivatives of δ-function. This expansion has been used
to expand the second virial co-efficientB
2 of the fluid. The expansion is correct up to the fourth power in thermal wavelength and the terms of the order of λ8 and λ4 in the first expa nsion are new. 相似文献
518.
The present paper is in two-fold. The first fold is devoted to the existence theory of equilibria for generalized abstract economy with a lower semicontinuous constraint correspondence and a fuzzy constraint correspondence defined on a noncompact/nonparacompact strategy set. In the second fold, we consider systems of generalized vector quasi-equilibrium problems for multivalued maps (for short, SGVQEPs) which contain systems of vector quasi-equilibrium problems, systems of generalized mixed vector quasi-variational inequalities and Debreu-type equilibrium problems for vector valued functions as special cases. By using the results of first fold, we establish some existence results for solutions of SGVQEPs. 相似文献
519.
G. Kbrich A. Akhtar F. Ansari W. E. Breckoff H. Büttner W. Drischel R. H. Fischer K. Flory H. Frhlich W. Goyert H. Heinemann I. Hornke H. R. Merkle H. Trapp W. Zündorf 《Angewandte Chemie (International ed. in English)》1967,6(1):41-52
Some years ago we found that α-halogenoorganolithium compounds (carbenoids) previously postulated as transient intermediates in organolithium-initiated α-eliminations can be obtained in a stable form. The present paper is a review of the methods for their preparation and of their reactivity. They possess both nucleophilic and electrophilic properties, which can be utilized singly or combained for the synthesis of substances of very different types. Their thermolability, which is considerably reduced (with only one known exception) by the solvent tetrahydrofuran, is due to electrophilic secondary reactions, in which carbenes evidently do not occur as intermediates. A mechanism is proposed which fits the experimental data for various carbenoid reactions. 相似文献
520.
The usual Strutinsky shell corrections include the pairing correlations in the BCS approach. At high-spin states the cranked intrinsic wave functions are not symmetric or antisymmetric under time reversal symmetry for general triaxial shapes. On the basis of the Hartree-Fock-Bogoliubov (HFB) approach two generalizations of the Strutinsky procedure are given to describe pairing correlations also for high-spin states and triaxial shapes. The method is applied to the neutron-deficient rare earth nucleus 150Gd. It is found that pairing has an important effect on the change of nuclear deformation with increasing angular momentum. The proton pairing persists at least up to I ≈ 40. 相似文献