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31.
Resinous materials, generally added to drying oils, were often employed as final protective films in paintings, both in tempera and oil techniques. Most of the resins used in fine arts come from exudates of plants. Natural resins are mainly composed by terpenoids. Among these resins, dammar, rosin, mastic, elemi gum, Venice turpentine were frequently employed in easel paintings. The aim of this work is the identification of natural resins in samples collected from works of art. In this paper we propose to use micro-FTIR spectrometry as a preliminary and non destructive technique to detect the presence of resinous materials in microsamples collected from paintings, followed by GC-MS analyses to obtain a precise identification of the resin. To reach this aim commercial resins, employed as standard, were analysed previously by micro-FTIR spectrometry and then analysed by GC-MS chromatography, searching characteristic chemical compounds used as "markers" of resins. The results obtained on standards allowed us to successfully analyse samples collected from two works of art: the "Portrait of a Young Gentleman", by Lorenzo Lotto (XVI century), and the "Madonna with the Infant Jesus and Saints": by Carlo Maratta (XVII secolo). 相似文献
32.
A new method of synthesizing the alkaloid aspidospermidine (1), based on building ring E on the pyridocarbazole [ABCD] ring structure, is reported. The preparation of the pyridocarbazole framework of Aspidosperma alkaloids is a new three-step synthetic application of 2-(1,3-dithian-2-yl)indoles. A tandem conjugate addition-alkylation reaction starting from indolyldithiane (4), 3-methylenelactam 6, and EtI yields the adduct 17. Treatment of lactam 17 with DIBALH leads to formation of the naphthyridoindole 18. Compound 18 isomerizes in aqueous AcOH to yield pyridocarbazole 3. Finally, closure of ring E and subsequent reduction of the dithiane ring produces aspidospermidine. Pyridocarbazoles 2 and 10 were prepared as models. 相似文献
33.
Three valency models for orthorhombic La2-x
Sr
x
CuO4 were investigated for increasing Sr concentrationsx (0x0.21): 1. Cu2+Cu3+, 2. apex O2–O– and 3. in-plane O2–O–. All calculations were done by using structural parameters valid for the temperature range from 10 to 22 K. We thereby calculated the electrostatic interaction energy which, next to ionization potentials and electron affinities, comprises a major of the binding energyE
B
of crystals. Second-order effects were accounted for by calculating the strength of ionic dipole moments induced by crystal electric fields at relevant lattice sites. Their largest strengths are comparable to the dipole moment of the water molecule. Three out of five dipoles in La2-x
Sr
x
CuO4 vanish during the transition from the orthorhombic to the tetragonal phase. The binding energy differences between the different models suggest that the system is in a state of model 1. However, the differences are very small, being in the order of 0.3 to 0.76 eV atx=0.13. 相似文献
34.
Mario Petrich 《Annali di Matematica Pura ed Applicata》1994,167(1):117-146
On the congruence lattice (2(5) of a completely regular semigroup S the following mappings are considered p: P and p: VP, whereP is any of the Green relationsH, L, R orD. The equivalence relationsP
andP
V induced by these maps represent the main object of study in the paper. The former is a complete -congruence whereas the latter is a complete congruence onC(S). In particularH
,H
V,L
V,R
V coincide with the kernel, trace, left trace and right trace relations onC(S), respectively. All essential properties known for the latter relations carry over to the new relationsP
andP
V. In addition, some interesting interplays of these provide for more richness in the theory of congruences on completely regular than is the case for the kernel-trace approach to congruences on regular semigroups. 相似文献
35.
We consider the linear heat equation in a domain occupied by a solid material with a network of pipes in which a well-mixed fluid is circulating. The temperature of the fluid in the pipe is uniform and its time variation is determined by the thermal flux on the wall of the pipe, plus a given internal source; continuity of the temperature across the pipe is also assumed. We suppose that we deal with a periodic geometry, with cells of size with inclusions of size rg; we study in detail in the case r, referring to a previous paper for the case r In the limit »0 we get a homogenized equation. The limit depends strongly on the ratio between the time variation of the temperature in the inclusions and the thermal flux through the interface. The homogenized equation has a new specific heat, which depends on the porosity and the constant of proportionality between the time variation of temperature and the flux on the boundary of the pipe. We also have a new thermal conductivity depending on the microstructure, and volume sources appear. The main tool is the energy method and we generalize the classical results for the more standard boundary conditions for parabolic equations. Finally, we consider the network of pipes forming a random ball structure. We prove convergence for this case. The homogenized equation is of the same form as in the periodic case but auxiliary problems are stochastic. 相似文献
36.
37.
Summary LetX be a centered stationary Gaussian stochastic process with ad-dimensional parameter (d2),F its spectral measure,
(x denotes the Euclidean norm ofx). We consider regularizations of the trajectories ofX by means of convolutions of the formX
(t)=(
*X)(t) where stands for an approximation of unity (as tends to zero) satisfying certain regularity conditions.The aim of this paper is to recover the local time ofX at a given levelu, as a limit of appropriate normalizations of the geometric measure of theu-level set of the regular approximating processesX
. A part of the difficulties comes from the fact that the geometric behavior of the covariance of the Gaussian processX
can be a complex one as approaches O.The results are onL
2-convergence and include bounds for the speed of convergence.L
presults may be obtained in similar ways, but almost sure convergence or simultaneous convergence for the various values ofu do not seem to follow from our methods. In Sect. 3 we have included examples showing a diversity of geometric behaviors, especially in what concerns the dependence on the thickness of the set in which the covariance of the original processX is irregular.Some technical results of analytic nature are included as appendices in Sect. 4. 相似文献
38.
Del Pópolo MG Lynden-Bell RM Kohanoff J 《The journal of physical chemistry. B》2005,109(12):5895-5902
Ab initio molecular dynamics simulations have been performed for the first time on the room-temperature organic ionic liquid dimethyl imidazolium chloride [DMIM][Cl] using density functional theory. The aim is to compare the local liquid structure with both that obtained from two different classical force fields and from neutron scattering experiments. The local structure around the cation shows significant differences compared to both the classical calculations and the neutron results. In particular, and unlike in the gas-phase ion pair, chloride ions tend to be located near a ring C-H proton in a position suggesting hydrogen bonding. The results are used to suggest ways in which the classical potentials may be improved. 相似文献
39.
Mario A. Natiello Gustavo E. Scuseria 《International journal of quantum chemistry》1984,26(6):1039-1049
Hartree-Fock equations are viewed as nonlinear algebraic equations that can be solved iteratively. Provided we assume the existence of a solution, valuable properties of convergence may be assessed. The close connection between convergence of the SCF procedure and stability properties of the solution is shown from a nonapproximate standpoint. The convergence features of level-shifting convergence-forcing techniques are analyzed. The connection between this nonlinear algebraic approach and the related gap equation is displayed and the example of the restricted Hartree-Fock hydrogen molecule is discussed. 相似文献
40.
Bendazzoli Gianni L. Raimondi Mario Garetz Bruce A. George Thomas F. Morokuma Keiji 《Theoretical chemistry accounts》1977,44(4):341-350
Semiclassical calculations are carried out by two methods for the problem of collision-induced predissociation of electronically excited I2. The first method is that of surface-hopping with the Landau-Zener model. The second method is similar to surface-hopping, except that analytic continuation of the adiabatic potential energy surfaces replaces the Landau-Zener model. Results of the calculations by the two methods compare favorably with each other and with experiment. The possible advantages of the second method are discussed.Camille and Henry Dreyfus Teacher-Scholar, Alfred P. Sloan Research Fellow. 相似文献