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61.
A computational study, in the framework of statistical kinetic theories, of the reaction of Ca2+ with urea has been carried out. The kinetically preferred products are NH3 + [CaOCNH]2+, which are the fifth products in order of stability. The second kinetically preferred products are , followed by [CaNH3]2++HNCO, whereas the most stable ones, and , appear only in residual quantities. These estimates are in agreement with the experimental evidence and provide a suitable mechanism to understand the competition between Coulomb explosion and neutral loss processes.  相似文献   
62.
We give, as L grows to infinity, an explicit lower bound of order \({L^{\frac{n}{m}}}\) for the expected Betti numbers of the vanishing locus of a random linear combination of eigenvectors of P with eigenvalues below L. Here, P denotes an elliptic self-adjoint pseudo-differential operator of order \({m > 0}\), bounded from below and acting on the sections of a Riemannian line bundle over a smooth closed n-dimensional manifold M equipped with some Lebesgue measure. In fact, for every closed hypersurface \({\Sigma}\) of \({\mathbb{R}^n}\), we prove that there exists a positive constant \({p_\Sigma}\) depending only on \({\Sigma}\), such that for every large enough L and every \({x \in M}\), a component diffeomorphic to \({\Sigma}\) appears with probability at least \({p_\Sigma}\) in the vanishing locus of a random section and in the ball of radius \({L^{-\frac{1}{m}}}\) centered at x. These results apply in particular to Laplace–Beltrami and Dirichlet-to-Neumann operators.  相似文献   
63.
The possibility of stabilizing the unstable acepentalene (acp) molecule through coordination to transition metals is investigated by means of DFT calculations. Comparison with related experimentally known pentalene complexes indicate that their acp homologues are just slightly less stable, suggesting that they could be synthesized and isolated. Other original mono- and trinuclear species, such as M(acp)2 (M = Zr, Hf), Co3(acp)2-, and Nb3(acp)2+, are also predicted to be stable.  相似文献   
64.
The novel cluster anion [Co(11)Te(5)(CO)15]- ([3]-) has been isolated and structurally characterized as part of the salt [Cp*(2)Nb(CO)2][3] (Cp* = C(5)Me(5)). The cobalt-centered Co10 pentagonal prism is surrounded by a shell of two mu5-Te, three mu4-Te ligands, and 15 CO groups in terminal, symmetrical, and sigma-semibridging bonding modes. The hybrid carbonyl-telluride character of the ligand shell is reflected in the solid state by a one-dimensional assembly of polyhedral prisms along a backbone of [Cp*(2)Nb(CO)2]+ cations. Electrochemical studies reveal the presence of four redox couples of [3]n (n = -1 to -5). The electronic structures of various metal-centered and empty pentagonal-prismatic (PP) M10 clusters (M = Co, Ni) are calculated and compared to those of pentagonal-antiprismatic (PA) M10 structures. Closed-shells of 152 and 156 metal valence electrons, respectively, are found to determine the electronic structures and chemical properties of these geometries. From these considerations, magnetic properties have been predicted. They have been verified for the [Co(11)Te(7)(CO)10]- cluster anion, which exhibits a singlet-triplet gap of 0.318 kcal/mol.  相似文献   
65.
We report on the synthesis of alkynyl ruthenium colorimetric sensors whose receptors are constituted by thiazolidinedione, rhodanine, or barbituric heads as recognition centers for anions. As modifications in the charge density at these recognition centers affect the whole molecule, through the alkynyl ligand acting as a communicating wire, the effects of hydrogen-bonding interactions with the anions were observed with the naked eye and monitored by UV-vis absorption spectrometry. The selectivity of the sensors was improved through electronic modifications of the alkynyl ruthenium subunit: the higher the electron density at the receptor head, the higher the selectivity is. TD-DFT calculations rationalize the long-range electronic communication as a main characteristic of the alkynyl ruthenium species and as a key to improve the selectivity of alkynyl ruthenium-based sensors toward anions.  相似文献   
66.
A new type of pH biosensor was developed for biological applications. This biosensor was fabricated using silicon microsystem technology and consists in two platinum microelectrodes. The first microelectrode was coated by an electrosynthesized polymer and acted as the pH sensitive electrode when the second one was coated by a silver layer and was used as the reference electrode. Then, this potentiometric pH miniaturized biosensor based on electrosynthesized polypyrrole or electrosynthesized linear polyethylenimine films was tested. The potentiometric responses appeared reversible and linear to pH changes in the range from pH 4 to 9. More, the responses were fast (less than 1 min for all sensors), they were stable in time since PPy/PEI films were stable during more than 30 days, and no interference was observed. The influence of the polymer thickness was also studied.  相似文献   
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69.
High molecular weight polymers have been prepared by ring-opening polymerization of propylene oxide PO using a Vandenberg initiator. Polymer electrolytes based on this polymer and an imide salt LiTFSI have been investigated. We present the results concerning the synthesis of the polymer and the glass transition temperatures evolution of the complexes with respect to salt composition. Diffusion constants of 19F and 7Li nuclei are determined by NMR techniques and a value of the cationic transport number t+ = 0.1 is obtained.  相似文献   
70.
Hafnia thin films for high-power optical coatings have been characterized by photoluminescence pumped by 4.66 eV photons and photothermal deflection measurements. These data are compared to the statistical laser damage behavior in order to find correlations between destructive and non-destructive characterizations. Thin films have been produced at two thicknesses and using different thin-film deposition techniques typically employed for optical coating fabrication: EBD (HfO2 target), EBD (Hf target), RLVIP and DIBS. The photoluminescence spectra show significant differences depending on the deposition techniques and thicknesses. EBD films show significant luminescence but the luminescence of ion-assisted films could not be distinguished from the uncoated substrate. All EBD coating spectra could be described by a linear combination of four bands. Further, XRD measurements show that the 255-nm-thick films had a relatively high crystallinity: EBD films contained the monoclinic phase and the ion-assisted films contained oriented nanocrystals of orthorhombic hafnia. The presence of orthorhombic phases indicates high compressive strain quenching the photoluminescence of these samples.  相似文献   
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