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991.
Recently a resonant Mie scattering (RMieS) correction approach has been developed and demonstrated to be effective for removing the baseline distortions that compromise the raw data in individual spectra. In this paper RMieS correction is extended to FTIR images of a tissue section from biopsy of the human cervical transformation zone and a coronal tissue section of a Wistar rat brain and compared to the uncorrected images. It is shown that applying RMieS correction to FTIR images a) removes baseline distortions from the image spectra and thus reveals previously hidden information on spatial variation of chemical contents within the tissue and b) can lead to improved automatic tissue feature classification through multivariate cluster analysis. 相似文献
992.
Generalized hydrodynamic moment hierarchies are derived which explicitly include nonequilibrium two-particle and higher-order correlations. The approach is adapted to strongly correlated media and nonequilibrium processes on short time scales which necessitate an explicit treatment of time-evolving correlations. Closure conditions for the extended moment hierarchies are formulated by a maximum-entropy approach, generalizing related closure procedures for kinetic equations. A self-consistent set of nonperturbative dynamical equations are thus obtained for a chosen set of single-particle and two-particle (and possibly higher-order) moments. Analytical results are derived for generalized Gaussian closures including the dynamic pair distribution function and a two-particle correction to the current density. The maximum-entropy closure conditions are found to involve the Kirkwood superposition approximation. 相似文献
993.
Meyer FM Collins JC Borin B Bradow J Liras S Limberakis C Mathiowetz AM Philippe L Price D Song K James K 《The Journal of organic chemistry》2012,77(7):3099-3114
A general method for constraining peptide conformations via linkage of aromatic sidechains has been developed. Macrocyclization of suitably functionalized tri-, tetra- and pentapeptides via Suzuki-Miyaura cross-coupling has been used to generate side chain to side chain, biaryl-bridged 14- to 21-membered macrocyclic peptides. Biaryl bridges possessing three different configurations, meta-meta, meta-ortho, and ortho-meta, were systematically explored through regiochemical variation of the aryl halide and aryl boronate coupling partners, allowing fine-tuning of the resultant macrocycle conformation. Suzuki-Miyaura macrocyclizations were successfully achieved both in solution and on solid phase for all three sizes of peptide. This approach constitutes a means of constraining peptide conformation via direct carbogenic fusion of side chains of naturally occurring amino acids such as phenylalanine and tyrosine, and so is complementary to strategies involving non-natural, for example, hydrocarbon, bridges. 相似文献
994.
K Searles M Pink KG Caulton DJ Mindiola 《Dalton transactions (Cambridge, England : 2003)》2012,41(32):9619-9622
The synthesis and characterization of a series of iridium(I) and iridium(III) complexes supported by a 3,5-bis(trifluoromethyl)-2-(2'-pyridyl)pyrrole (L(-)) ligand are reported. Compound [Ir(L)(COD)] (COD = 1,5-cyclooctadiene) demonstrates reversible binding of hydrogen to form a dihydride complex [Ir(L)(H)(2)(COD)] with no hydrogenation of COD. 相似文献
995.
AS Chesman DR Turner KJ Berry NF Chilton B Moubaraki KS Murray GB Deacon SR Batten 《Dalton transactions (Cambridge, England : 2003)》2012,41(37):11402-11412
The isostructural heterometallic complexes [Ln(III)(2)Mn(III)(2)O(2)(ccnm)(6)(dcnm)(2)(H(2)O)(2)] (Ln = Eu (1Eu), Gd (1Gd), Tb (1Tb), Er (1Er); ccnm = carbamoylcyanonitrosomethanide; dcnm = dicyanonitrosomethanide) have been synthesised and structurally characterised. The in situ transition metal promoted nucleophilic addition of water to dcnm, forming the derivative ligand ccnm, plays an essential role in cluster formation. The central [Ln(III)(2)Mn(III)(2)(O)(2)] moiety has a "butterfly" topology. The coordinated aqua ligands and the NH(2) group of the ccnm ligands facilitate the formation of a range of hydrogen bonds with the lattice solvent and neighbouring clusters. Magnetic measurements generally reveal weak intracluster antiferromagnetic coupling, except for the large J(MnMn) value in 1Gd. There is some evidence for single molecule magnetic (SMM) behaviour in 1Er. Comparisons of the magnetic properties are made with other recently reported butterfly-type {Ln(III)(x)M(III)(4-x) (d-block)} clusters, x = 1, 2; M = Mn, Fe. 相似文献
996.
Khalid A‐Alamry Keith Nixon Rachel Hindley Jeffrey A. Odel Stephen G. Yeates 《Macromolecular rapid communications》2011,32(3):316-320
We report for the first time evidence of flow‐induced polymer degradation during inkjet printing for both poly(methyl methacrylate) (PMMA) and polystyrene (PS) in good solvent. This has significance for the deposition of functional and biological materials. Polymers having either less than 100 kDa or greater than approximately 1 000 kDa show no evidence of molecular weight degradation. The lower boundary condition is a consequence of low Deborah Number De imposed by the printhead geometry and the upper boundary condition due to visco‐elastic damping. For intermediate molecular weights the effect is greatest at high elongational strain rate and low solution concentration with higher polydispersity polymers being most sensitive to molecular weight degradation. For low polydispersity samples, PDi ≤ 1.3, chain breakage is essentially centro‐symmetric induced either by turbulance or overstretching when the strain rate increases well beyond a critical value, that is the stretching rate is high enough to exceed the rate of relaxation. For higher polydispersity samples chain breakage is consistent with almost random scission along the chain, inferring that the forces required to break the chain are additionally transmitted either by valence bonds, i.e. network chains and junctions or discrete entanglements rather than solely by hydrodynamic interaction.
997.
Tracey M. McLean Deidre Cleland Keith C. Gordon Shane G. Telfer Mark R. Waterland 《Journal of Raman spectroscopy : JRS》2011,42(12):2154-2164
Detailed studies of the mechanism of surface‐enhanced (resonance) Raman spectroscopy (SE(R)RS), and its applications, place a number of demands on the properties of SERS scatterers. With large Raman cross‐sections, versatile synthetic chemistry and complete lack of fluorescence, free dipyrrins meet these demands but the Raman and SE(R)RS spectroscopy of free dipyrrins is largely unknown. The first study of the Raman spectroscopy of free dipyrrins is therefore presented in this work. The nonresonant Raman, resonant Raman and surface‐enhanced Raman spectra of a typical meso aryl‐substituted‐dipyrrin are reported. Absolute differential cross‐sections are obtained for excitation wavelengths in the near infrared and visible region, in solution phase and for dipyrrin adsorbed on the surface of silver nanoparticles. Raman enhancement factors for SERRS and resonance Raman are calculated from the observed differential cross‐sections. The magnitudes of the resonantly enhanced cross‐sections are similar to those recently reported for strong SERS dyes such as Rhodamine 6G and Crystal Violet. Free dipyrrins offer the advantages of existing SERS dyes but without the drawback of strong fluorescence. Free dipyrrins should therefore find applications in all areas of Raman spectroscopy including fundamental studies of the mechanisms of SERS and bioanalytical and environmental applications. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
998.
Keith A. Olive 《Brazilian Journal of Physics》2013,43(5-6):320-327
The last 2 years has seen an immense amount of activity and results from the Large Hadron Collider (LHC). Most notable is the discovery of a new particle which may very well be the long sought Higgs boson associated with electroweak symmetry breaking. There have also been many (up to now) unsuccessful searches for new particles associated with supersymmetry. One of the most attractive candidates for dark matter is the lightest supersymmetric particle (LSP). The recent results from the LHC have had a dramatic impact on our expectations for the properties of the LSP. These results can be used to revise expectations for both direct and indirect detection of dark matter. 相似文献
999.
We consider the extension of the standard single-determinant Kohn–Sham method to the case of a multi-configuration auxiliary wave function. By applying the rigorous Kohn–Sham method to this case, we construct the proper interacting and auxiliary energy functionals. Following the Hohenberg–Kohn theorem for both energy functionals, we derive the corresponding multi-configuration Kohn–Sham equations, based on a local effective potential. At the end of the analysis we show that, at the ground state, the auxiliary wavefunction must collapse into a single-determinant wave function, equal to the regular KS wavefunction. We also discuss the stability of the wavefunction in multi-configuration density functional theory methods where the auxiliary system is partially interacting, and the remaining (residual) correlation is evaluated as a functional of the density. As an example showing both the challenges and the possibilities, we implement such a procedure for the perfect pairing wavefunction, using a residual correlation functional that is based on the Lee–Yang–Parr functional, and present results for an elementary bond-breaking process. 相似文献
1000.
Local active space correlation models based on the coupled-cluster doubles (CCD) model like Generalized Valence Bond Perfect Pairing (GVB-PP) and Imperfect Pairing (IP) are attractive methods for treating electron correlation, because they are computationally inexpensive and can describe strong correlations. However, they suffer from symmetry-breaking (SB) in systems with multiple resonance structures, which arises due to neglected correlations. We investigate the extent to which these problems can be removed by using second-order perturbation theory (PT) for weak correlations coupling three different electron pairs, and (infinite-order) coupled-cluster (CC) theory for stronger correlations involving electrons in only one or two pairs. The resulting Three-Pair Corrected Imperfect Pairing (TIP) method is explored here, and it is shown that to robustly combine CC and PT it is necessary to modify several aspects of the basic method. Most importantly, a penalty function term is introduced to ensure the PT amplitudes remain small. Comparison against CC treatment of the three-pair correlations suggests penalty terms will be beneficial for any hybrid CC/PT method that includes orbital optimization. The TIP method greatly reduces SB in aromatic hydrocarbons and recovers a significantly higher fraction of the valence electron correlation energy than IP. 相似文献