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21.
Calculation of the rotational barriers for the trans- and cis-forms of 2-(p-methoxy)-1-acetyl-pyrroline are presented in this paper. It is found that thetrans-isomer is slightly more favourable energetically, while the rotations of the cis-form are highly impeded. Hence the relevant rotations are in thetrans-form which stabilizes its energy by forming a weak inner proton bond between the carbonyl oxygen and the pyrroline ring. The acetyl rotational barrier is of the order of 8 kcal, which is well in accord with experimental data reported in the literature for other acetyl-amide derivatives.[/p]Work supported in part by Instituto Mexicano del Petróleo. 相似文献
22.
Using a very simple trial function and unperturbed electron densities calculated by a new procedure, the frequency-dependent dipole polarizability () of Ne, Ar, Kr and Xe has been calculated in the range 0 0.45 a.u., by a Karplus-Kolker-type variation-perturbation method. Results progressively worsen for larger systems so that, for Xe, (0) is only 75% of the experimental value. Probable reasons for this are discussed. 相似文献
23.
Tohru Nishinaga 《Tetrahedron》2004,60(15):3375-3382
A series of hexadehydro[18]annulenes fused with different numbers of p-benzoquinone, 4-6, were synthesized by stepwise transformation of the p-dimethoxybenzene moiety of the precursor dehydroannulene 3 fused with three 3,6-dimethoxy-4,5-dimethylbenzene units at 1,2-positions into p-benzoquinone using ceric ammonium nitrate. The UV-vis spectra of compounds 4 and 5, which have both electron-donating p-dimethoxybenzene unit(s) and electron-accepting p-benzoquinone unit(s) in the π-systems, showed the maximum absorption bands bathochromically shifted in comparison with 3 having only p-dimethoxybenzene units and 6 having only p-benzoquinone units. However, the solvatochromism expected for 4 and 5 was found to be quite weak possibly because the HOMO and LUMO (B3LYP/6-31G(d)) are not localized but rather delocalized over the whole π-systems. 相似文献
24.
Two methods are proposed, one for the location of saddle points and one for the calculation of steepest-descent paths on multidimensional surfaces. Both methods are based on a constrained simplex optimization technique that avoids the evaluation of gradients or second derivative matrices. Three chemical reactions of increasing structural complexity are studied within the PRDDO SCF approximation. Predicted properties of reaction hypersurfaces are in good overall agreement with those determined by gradient minimization and gradient following algorithms in connection with various ab initio SCF methods. Computational efforts required by the new procedures are discussed. 相似文献
25.
《Journal of fluorine chemistry》2002,113(2):147-154
Equilibrium structures of isolated fluorolithiomethanes (1-3), chlorofluorolithiomethanes (4-6), bromofluorolithiomethanes (7-9), and bromochlorofluorolithiomethane (10) have been calculated at the HF/6-31+G(d,p) and MP2/6-31+G(d,p) levels. Depending on the number of halogens and the computational method employed, five distinct minimum structures could be recognized, viz. normal tetrahedral without coordination of halogen (T), trigonal bidentate with coordination of carbon and halogen to lithium (BCX), tetrahedral tridentate with coordination of carbon and two halogens to lithium (TCX2), quadrilateral bidentate with coordination of two halogens to lithium (BX2), and bipyramidal tridentate with coordination of three halogens to lithium (TX3). 相似文献
26.
The structures of B32 and B32H2–32 with Ih symmetry have been investigated by means of ab initio calculations at STO-3G level. The relationship between molecular orbitals of them has been analyzed and their bonding properties have been discussed. Then the possibility of their existence, as well as the similarity and difference between B32 (B32H2–32) and C60 (C60H60) have been inferred. 相似文献
27.
Silyleneisthesimilarityofsilicontocarbene,and,likecarbeneinorganicreactions,itplaysaveryimportantroleinorganosiliconreactions.Inrecentyears,therehavebeenmanyreportsonsilylenesinquantumchemicalresearches[1—3].Investigationonitsorganicreactionshowsthatreali… 相似文献
28.
Arrhenius parameters values, in non-isothermal kinetic vaporisation processes for a series of compounds with related structures,
have been calculated. This was made using a method of calculation that allows to find the most probable vaporisation mechanisms.
According to this method DTG curves were compared with some theoretical ones reported in literature, whose shape results to
be only a function of the mechanisms. In this way the choice of the mathematical functions which can be inserted in the kinetic
equations, was influenced by the shape of the DTG plots and other thermal analysis signals thus allowing to choose the most
probable mechanisms.
The kinetic parameters derived from these mechanisms were compared, using statistical analysis, with those obtained from another
method of calculation based on ‘a priori’ vaporisation mechanism chosen for the investigated liquid–gas transition.
The standard deviations of the slope and of the intercept, together with the standard deviation and the square correlation
coefficient (r
2) of the linear regression equations related to the mechanisms of the two methods were calculated. Student t-test, Fisher F-test, confidence intervals (c.i.) and residuals valueswere also given.
Statistical analysis shows that the mechanisms obtained with the former method (diffusive and geometrical models) and the
related Arrhenius parameters result to be more significant (in terms of probability) than the corresponding quantities of
the latter for which a first-order model was chosen.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
29.
30.
GUO Jian-Jun YANG Ji-Xian DIE Dong 《理论物理通讯》2007,48(2):348-352
The first-principles method based on density-functional theory is used to investigate the geometries of the lowest-lying isomers of AunAg2 (n = 1 - 4) clusters. Several low-lying isomers are determined, and many of them in electronic configurations with a high spin multiplicity. The stability trend of Ag-doped Aun dusters is compared to that of pure Aun clusters. Our results indicate that the inclusion of two Ag atoms in the clusters lowers the cluster stability, indicating higher stability as the structures grow in size. The bigger energy difference between the Aun and AunAg2 curves as the structures grows in size. This information will be useful to understanding the enhanced catalytic activity and selectivity gained by using silver-doped gold catalyst. 相似文献