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941.
María Carolina dos Ramos 《Molecular physics》2013,111(10):1349-1365
We have used the hetero-SAFT-VR approach developed by McCabe and collaborators [Mol. Phys. 104, 571 (2006)] to investigate the phase equilibria of a number of binary and ternary mixtures of n-alkanes, perfluoro-n-alkanes, and perfluoroalkylalkane diblock surfactants. We focused our work on the understanding of the microscopic conditions that control the phase behaviour of these mixtures, with a particular emphasis of the effect on the liquid–liquid separation and the stabilisation of n-alkane + perfluoro-n-alkane mixtures when a diblock surfactant is added. We used very simple molecular models for n-alkanes, and perfluoro-n-alkanes that describe the molecules as chains with tangentially bonded segments with molecular parameters taken from the literature. In the particular case of semifluorinated alkanes or SFA surfactants, we used an hetero-segmented diblock chain model where the parameters for the alkyl and perfluoroalkyl segments taken from the corresponding linear alkanes and perfluoroalkanes, as shown in our previous work [J. Phys. Chem. B 111, 2856 (2007)]. Our goal was to identify the main effects on the phase behaviour when different perfluoroalkylalkane surfactants are added to mixtures of n-alkanes and perfluoro-n-alkanes. We selected the n-heptane + perfluoromethane binary mixture, and studied the changes on the phase behaviour when a symmetric (same number of alkyl and perfluoroalkyl chemical groups) or an asymmetric (different number of alkyl and perfluoroalkyl chemical groups) diblock surfactants is added to the binary mixture. We have obtained the phase diagrams of a wide range of binary and ternary mixtures at different thermodynamic conditions. We have found a variety of interesting behaviours as we modify the alkyl or/and the perfluoroalkyl chain-length of the diblock surfactants: the usual changes in the vapour–liquid phase separation, changes in the type of phase diagrams (typically from type I to type V phase behaviour according to the Scott and Konynenburg classification), azeotropy, and Bancroft points. We noted that the main effect of adding a symmetric or an asymmetric surfactant to the n-heptane + perfluoromethane mixture is to stabilise the system, i.e. to decrease the two-phase (liquid–liquid) immiscibility region of the ternary diagram as the surfactant concentration is increased. This effect becomes larger as the chain length of the surfactant is increased, which is consistent with a higher number of alkyl–alkyl and perfluoroalkyl–perfluoroalkyl favourable interactions in the mixture. 相似文献
942.
The diazocarbene radical, CNN, and the ions CNN+ and CNN? were investigated at a high level of theory. Very accurate structural parameters for the states X 3Σ? and A 3Π of CNN, and X 2Π of both CNN+ and CNN? were obtained with the UCCSD(T) method using correlated-consistent basis functions with extrapolations to the complete basis set limit, with valence only and also with all electrons correlated. Harmonic and anharmonic frequencies were obtained for all species and the Renner parameter and average frequencies evaluated for the Π states. At the UCCSD(T)/CBST-5 level of theory, Δf H(0 K) = 138.89 kcal/mol and Δf H(298 K) = 139.65 kcal/mol were obtained for diazocarbene; for the ionization potential and the electron affinity of CNN, 10.969 eV (252.95 kcal/mol), and 1.743 eV (40.19 kcal/mol), respectively, are predicted. Geometry optimization was also carried out with the CASSCF/MRCI/CBST-5 approach for the states X 3Σ?, A 3Π, and a 1Δ of CNN, and with the CASSCF/MRSDCI/aug-cc-pVTZ approach for the states b 1Σ+, c 1Π, d 1Σ?, and B 3Σ?, and excitation energies (Te) evaluated. Vertical energies were calculated for 15 electronic states, thus improving on the accuracy of the five transitions already described, and allowing for a reliable overview of a manifold of other states, which is expected to guide future spectroscopic experiments. This study corroborates the experimental assignment for the vertical transition X 3Σ? ← E 3Π. 相似文献
943.
Irene Brito M. F. A. da Silva Filipe C. Mena N. O. Santos 《General Relativity and Gravitation》2013,45(2):519-530
We investigate the matching, across cylindrical surfaces, of static cylindrically symmetric conformally flat spacetimes with a cosmological constant $\Lambda $ , satisfying regularity conditions at the axis, to an exterior Linet–Tian spacetime. We prove that for $\Lambda \le 0$ such matching is impossible. On the other hand, we show through simple examples that the matching is possible for $\Lambda >0$ . We suggest a physical argument that might explain these results. 相似文献
944.
Hans Adriaensen Maja Musse Stéphane Quellec Alexandre Vignaud Mireille Cambert François Mariette 《Magnetic resonance imaging》2013
The transverse relaxation signal from vegetal cells can be described by multi-exponential behaviour, reflecting different water compartments. This multi-exponential relaxation is rarely measured by conventional MRI imaging protocols; mono-exponential relaxation times are measured instead, thus limiting information about of the microstructure and water status in vegetal cells. In this study, an optimised multiple spin echo (MSE) MRI sequence was evaluated for assessment of multi-exponential transverse relaxation in fruit tissues. The sequence was designed for the acquisition of a maximum of 512 echoes. Non-selective refocusing RF pulses were used in combination with balanced crusher gradients for elimination of spurious echoes. The study was performed on a bi-compartmental phantom with known T2 values and on apple and tomato fruit. T2 decays measured in the phantom and fruit were analysed using bi- and tri-exponential fits, respectively. The MRI results were compared with low field non-spatially resolved NMR measurements performed on the same samples. 相似文献
945.
S. L. C. Ferreira H. S. Ferreira G. D. Matos D. S. Anunciação W. N. L. dos Santos V. P. Campos 《应用光谱学评论》2013,48(8):633-653
Abstract: This article presents a critical evaluation of the analytical procedures used for the determination of lead in seawater, which is important because lead is a good indicator of marine pollution caused by human activities. Sampling, storage, and pretreatment techniques are briefly overviewed, including the significance of systematic errors that cannot be corrected later on. The main techniques in this article are electrothermal–atomic absorption spectrometry (ET-AAS), inductively coupled plasma–mass spectrometry (ICP-MS), and voltammetry. Flame atomic absorption spectrometry (FAAS) and inductively coupled plasma–optical emission spectrometry (ICP-OES) are treated as well, although their limits of quantification are not sufficient for a determination of lead in unpolluted seawater. Even when separation and preconcentration techniques are applied, these techniques are only capable of detecting lead in polluted coastal seawater. Separation and preconcentration are actually also required for ET-AAS and ICP-MS in order to determine the lowest concentrations of lead found in unpolluted open-ocean seawater, which is still a challenge for the analytical chemist. 相似文献
946.
Mirian C. Santos 《应用光谱学评论》2013,48(4):427-448
Abstract This review summarizes and discusses the preparation of slurries for analysis of inorganic materials by inductively coupled plasma optical emission spectrometry (ICP‐OES) and inductively coupled plasma mass spectrometry (ICP‐MS). Details about the grinding step for slurry preparation, the stabilization of slurries, and the calibration strategies are critically discussed. Typical applications described in the literature and the state‐of‐the‐art including advantages and limitations of slurry analysis are presented. 相似文献
947.
Maria das Graças Andrade Korn Elane Santos da Boa Morte Daniele Cristina Muniz Batista dos Santos Jacira Teixeira Castro José Tiago Pereira Barbosa Alete Paixão Teixeira 《应用光谱学评论》2013,48(2):67-92
Abstract The present article gives an overview of recent publications and modern techniques of sample preparation for food analysis employing atomic and inorganic mass spectrometric techniques, such as flame atomic absorption spectrometry, chemical vapor generation atomic absorption and atomic fluorescence spectrometry, graphite furnace atomic absorption spectrometry, inductively coupled plasma optical emission spectrometry, and inductively coupled plasma mass spectrometry. Among the most frequently applied sample preparation techniques for food analysis are dry ashing, usually with the addition of an ashing aid, and acid digestion, preferably with the assistance of microwave energy. Slurry preparation, particularly with the assistance of ultrasound, is increasingly used to reduce acid consumption and sample preparation time. Direct analysis of solid samples is gaining importance in the field of food analysis as it offers the highest sensitivity, avoids the use of acids and other aggressive reagents, makes possible the analysis of micro‐samples, and can be applied for fast screening analysis, e.g., of fresh meat. 相似文献
948.
Single crystalline SrTiO 3 samples were implanted with Er ions of 150 v keV at room temperature with fluences of 5 ‐ 10 14 and 5 ‐ 10 15 . Annealing treatments were carried out both in reducing and oxidising atmospheres to recover the implantation damage. Infrared 1.54 v m Er 3+ luminescence between the two lowest spin-orbit levels 4 I 13/2 M 4 I 15/2 as well as emission from higher excited states 4 S 3/2 M 4 I 15/2 , 4 F 9/2 M 4 I 15/2 and 4 S 3/2 M 4 I 13/2 were observed in the implanted samples with highest fluence, annealed either in air or in vacuum. Multiple site location of Er 3+ ion is discussed and compared with RBS/C and emission channelling results that indicate that Er goes to Sr and Ti sites. 相似文献
949.
950.
We present a unified framework for constructing the globally convergent algorithms for a broad class of multidimensional coefficient inverse problems arising in natural science and industry. Based on the convexification approach, the unified framework substantiates the numerical solution of the corresponding problem of nonconvex optimization. A globally convergent iterative algorithm for an inverse problem of diffuse optical mammography is constructed. It utilizes the contraction property of a nonlinear operator resulting from applying the convexification approach. The effectiveness of this algorithm is demonstrated in computational experiments. 相似文献