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61.
Based on the local density approximation (LDA) in the framework of the density-functional theory, we study the details of electronic structure, energetics and geometric structure of the chiral carbon nanotubes. For the electronic structure, we study all the chiral nanotubes with the diameters between 0.8 and 2.0 nm (154 nanotubes). This LDA result should give the important database to be compared with the experimental studies in the future. We plot the peak-to-peak energy separations of the density of states (DOS) as a function of the nanotube diameter (D). For the semiconducting nanotubes, we find the peak-to-peak separations can be classified into two types according to the chirality. This chirality dependence of the LDA result is opposite to that of the simple π tight-binding result. We also perform the geometry optimization of chiral carbon nanotubes with different chiral-angle series. From the total energy as a function of D, it is found that chiral nanotubes are less stable than zigzag nanotubes. We also find that the distribution of bond lengths depends on the chirality. 相似文献
62.
FEA calculations have been carried out for a model rubber shear spring, consisting of a block of a highly elastic material, bonded between two rigid parallel plates and sheared by displacing one of the plates parallel to the other in its own plane. The block was prevented from deforming in the perpendicular direction, and thus was deformed in plane strain. Stress distributions along the bond-line and the center-line are reported and compared with those expected from the theory of large elastic deformations. Unexpected tensile stresses were found to develop in the interior of the sheared block. They are attributed to the absence on the end surfaces of the stresses needed to maintain a simple shear, causing a pronounced change in the reference pressure—a consequence that is usually overlooked. Because the internal stresses are governed by the boundary conditions, they were strongly affected by the shape of the end surfaces. In addition, they were reduced markedly by assigning values to Poisson's ratio slightly lower than 0.5, thus allowing some volume expansion of the rubber. Strain energy release rates were also evaluated for growth of a crack along the bond-line, starting at the edges, and compared with those reported previously by Lindley and Teo [Energy for crack growth at the bonds of rubber springs, Plast. Rubber Mat. Appl. 4 (1979) 29-37], Muhr et al. [A fracture mechanics study of natural rubber-to-metal bond failure, J. Adhes. Sci. Technol. 10 (1996) 593-616], Gregory and Muhr [Stiffness and fracture analysis of bonded rubber blocks in simple shear, in: D. Boast, V.A. Coveny (Eds.), Finite Element Analysis of Elastomers, Professional Engineering Publications, Bury St. Edmunds, UK, 1999, pp. 265-274] and Gough and Muhr [Initiation of failure of rubber close to bondlines, in: Proceedings of the International Rubber Conference, Maastricht, Netherlands, June 2005, IOM Communications Ltd., London, 2005, pp. 165-174]. They confirm that a long crack at the compression edge will grow faster than one at the tension edge, but the results for short cracks were inconclusive. 相似文献
63.
Two Hexagonal Series of Lanthanoid(III) Oxide Fluoride Selenides: M6O2F8Se3 (M = La – Nd) and M2OF2Se (M = Nd,Sm, Gd – Ho) 下载免费PDF全文
Dirk D. Zimmermann Hagen Grossholz Sarah Wolf Oliver Janka Alexander C. Müller Thomas Schleid 《无机化学与普通化学杂志》2015,641(11):1926-1933
Two hexagonal series of lanthanoid(III) oxide fluoride selenides with similar structure types can be obtained by the reaction of the components MF3, M2O3, M, and Se in sealed niobium tubes at 850 °C using CsI as fluxing agent. The compounds with the lighter and larger representatives (M = La – Nd) occur with the formula M6O2F8Se3, whereas with the heavier and smaller ones (M = Nd, Sm, Gd – Ho) their composition is M2OF2Se. For both systems single‐crystal determinations were used in all cases. The compounds crystallize in the hexagonal crystal system (space group: P63/m) with lattice parameters of a = 1394–1331 pm and c = 403–372 pm (Z = 2 for M6O2F8Se3 and Z = 6 for M2OF2Se). The (M1)3+ cations show different square antiprismatic coordination spheres with or without an extra capping fluoride anion. All (M2)3+ cations exhibit a ninefold coordination environment shaped as tricapped trigonal prism. In both structure types the Se2– anions are sixfold coordinated as trigonal prisms of M3+ cations, being first condensed by edges to generate trimeric units and then via faces to form strands running along [001]. The light anions reside either in threefold triangular or in fourfold tetrahedral cationic coordination. For charge compensation, both structures have to contain a certain amount of oxide besides fluoride anions. Since F– and O2– can not be distinguished by X‐ray diffraction, bond‐valence calculations were used to address the problem of their adjunction to the available crystallographic sites. 相似文献
64.
A novel method for achieving a copper(II)-catalyzed domino reaction for the construction of 2-aryl quinazolinones,without the addition of any ligand and additive,has been developed.The domino reaction achieved N-(a-substituted)benzylation,benzylic C–H amidation,and C–C(or C–H) bond cleavage. 相似文献
65.
Bond Dissociation Energies and Electronic Structures in a Series of Peroxy Radicals: A Theoretical Study 下载免费PDF全文
Quantum chemical calculations are performed to estimate the bond dissociation energies (BDEs) for 18 peroxy radicals. Since DFT methods are researched to have low basis sets sensitivity, these radicals are studied by utilizing the hybrid density functional theory (DFT) (B3LYP, B3P86, B3PW91 and PBE1PBE) in conjunction with the 6‐311G** basis set and the complete basis set (CBS‐Q) method. On the basis of comparisons of the computational results and the experimental values, we evaluate the effectiveness of above methods. It is demonstrated that CBS‐Q method is the best method for computing the reliable BDEs of C—OO bond, with the average absolute errors of 2.1 kcal/mol. So CBS‐Q method is suitable to predict accurate BDEs of C‐OO bond for peroxy compounds. The computational energy gaps between the HOMO and LUMO of studied compounds are almost identical from the point of view of stability and substantial HOMO‐LUMO gaps for all molecules suggest their electronic stability. In addition, substituent effect on the C—OO BDE of peroxy radicals is analyzed. It is noted that the effects of substitution on the C—OO BDE of peroxy radicals are significant. Our results will shed lights on future theoretical and experimental work. 相似文献
66.
Mode Specificity,Bond Selectivity,and Product Energy Disposal in X + CH4/CHD3 (X=H,F, O(3P), Cl,and OH) Hydrogen Abstraction Reactions: Perspective from Sudden Vector Projection Model 下载免费PDF全文
Reactions between methane and various radicals have become the workhorse in our understanding of mode specificity and bond selectivity in bimolecular reactions. In this work, the recently proposed Sudden Vector Projection (SVP) model is used to gain insight into the existing experimental and theoretical data on these reactions. The SVP model attributes mode specificity and bond selectivity to the coupling of reactant modes/bonds with the reaction coordinate at the transition state. In the sudden limit, the strength of the coupling can be simply computed by projecting the corresponding reactant normal mode vector onto that of the imaginary frequency mode at the saddle point. In addition, the SVP model can be used to predict energy disposal in the products, thanks to microscopic reversibility. It is shown that most of the mode‐specific and bond‐selective chemistry in X + CH4/CHD3 (X=H, F, O(3P), Cl, and OH) reactions can be reasonably understood with this simple model. 相似文献
67.
A new scheme, called "list of nonredundant bonds", is presented to record the number of bonds and their positions for the atoms involved in Kekulé valence structures of (poly)cyclic conjugated systems. Based on this scheme, a recursive algorithm for generating Kekulé valence structures has been developed and implemented. The method is general and applicable for all kinds of (poly)cyclic conjugated systems including fullerenes. The application of the algorithm in generating Valence Bond (VB) wave functions, in terms of Kekulé valence structures, is discussed and illustrated in actual VB calculations. Two types of VBSCF calculations, one involving Kekulé valence structures only and the second one involving all covalent VB structures, were performed for benzene, pentalene, benzocyclobutadiene, and naphthalene. Both strictly local and delocalised p-orbitals were used in these calculations. Our results show that, when the orbitals are restricted to their own atoms, other VB structures (Dewar structures) also have a significant contribution in the VB wave function. When removing this restriction, the other VB structures (Dewar and also the ionic structures) are accommodated in the Kekulé valence structures, automatically. Therefore, at VBSCF delocal level, the ground states of these systems can be described almost quantitatively by considering Kekulé valence structures only at a considerable saving of time. 相似文献
68.
Daisuke Sasaki Yoshihiro Suzuki Hagiwara Toshiki Shoichiro Yano Takashi Sawaguchi 《Journal of Analytical and Applied Pyrolysis》2007,80(2):312-318
The reactive end groups of nonvolatile oligomers obtained by controlled thermal degradation of poly(propylene-ran-ethylene) and poly(propylene-ran-1-butene) were determined by 1H and 13C NMR spectroscopy. The molar ratio of unsaturated to saturated end groups was found to be about 9:1. The average number of unsaturated end groups per molecule was between 1.6 and 1.8, indicating that 60–80 mol% of the oligomer molecules were telechelic, having two terminal unsaturated end groups. These oligomers had a lower polydispersity than the raw material, despite their lower molecular weight and melting temperature. Although the end groups resulting from each monomer unit could be detected by 13C NMR, the end group composition differed from that of the main chains of the raw materials. The end group composition was satisfactorily explained by the differences in bond dissociation energy and activation energy of elementary reactions that occurred during thermal degradation, based on the monomer composition of the raw materials. 相似文献
69.
Carbon fiber-reinforced plastic (CFRP) reinforced concrete beams can fail due to interface debonding, due to the high tensile
strength of such rebars. A set of 16 concrete beams reinforced with different amounts of CFRP reinforcement was subject to
static three-point bending. The beam dimensions and CFRP reinforcements used were selected to demonstrate a transition from
compression failure to bond failure with decreasing reinforcement ratio. It is shown that accurate bond strength data to predict
such failures can be obtained from a “hinged-beam” test configuration, rather than the conventional direct “pull-out” tests.
Deflection under service loads can also be predicted more accurately using a proposed equation that includes the reinforcement
ratio and the elastic modulus of the reinforcement. 相似文献
70.
建立了紧束缚近似下的二嵌段共聚物-(A)x-(B)y-的物理模型,研究了组成共聚物的均聚物间界面相互作用-界面耦合的强弱对共聚体系的能带结构、键结构性质等的影响.共聚物的带隙也可通过改变均聚物之间的界面相互作用来加以调制,进一步发现可用界面势阱或能垒(energy barrier)来表征界面耦合的强弱. 相似文献