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41.
In some one-dimensional chains with metallic band structures the energetically most advantageous distortion opens an energy gap non-linear in the distortion. The absence of a linear Peierls effect is due to the symmetry of the degenerate pair of orbitals at the Fermi level: they do not interact directly in the distorted system. The effect provides a natural bridging of the one-dimensional polyacetylene (linearly Peierls-distorted) to the two-dimensional graphite (not distorted) carbon skeletons. The simple explanation bears some generality. 相似文献
42.
Determination of the expected decrease in strength of high alumina cement concrete by derivatography
Methods involving the use of the derivatograph in the determination of the expected decrease in strength of high alumina cement are described. In a series of steps the strength, porosity and the cement content of the concrete are determined by physico-chemical measurements. The actual phase composition of the cement component of concrete is determined by derivatography. Methods of separating the two overlapping peaks due to the dehydration of the calcium aluminate hydrates present in the cement are described. 相似文献
43.
The collection of a low vapor pressure chemical simulant triethyl phosphate sorbed onto silica gel (TEP/SG) from a surface with subsequent analysis of the TEP/SG particulates using desorption electrospray ionization–mass spectrometry (DESI–MS) is described. Collection of TEP/SG particulates on a surface was accomplished using a sticky screen sampler composed of a stainless steel screen coated with partially polymerized polydimethylsiloxane (PDMS). DESI–MS analysis of TEP/SG particulates containing different percentages of TEP sorbed onto silica gel enabled the generation of response curves for the TEP ions m/z 155 and m/z 127. Using the response curves the calculation of the mass of TEP in a 25 wt% sample of TEP/SG was calculated, results show that the calculated mass of TEP was 14% different from the actual mass of TEP in the sample using the m/z 127 TEP ion response curve. Detection limits for the TEP vapor and TEP/SG particulates were calculated to be 4 μg and 6 particles, respectively. 相似文献
44.
Miklos Abert Nicolas Bergeron Ian Biringer Tsachik Gelander Nikolay Nikolov Jean Raimbault Iddo Samet 《Comptes Rendus Mathematique》2011,349(15-16):831-835
We announce new results concerning the asymptotic behavior of the Betti numbers of higher rank locally symmetric spaces as their volumes tend to infinity. Our main theorem is a uniform version of the Lück Approximation Theorem (Lück, 1994 [10]) which is much stronger than the linear upper bounds on Betti numbers given by Gromov in Ballmann et al. (1985) [3].The basic idea is to adapt the theory of local convergence, originally introduced for sequences of graphs of bounded degree by Benjamini and Schramm, to sequences of Riemannian manifolds. Using rigidity theory we are able to show that when the volume tends to infinity, the manifolds locally converge to the universal cover in a sufficiently strong manner that allows us to derive the convergence of the normalized Betti numbers. 相似文献
45.
On the basis of a thorough Cambridge Structural Database survey, we present a statistical analysis of the packing of TCNQ anion pi-radicals in TCNQ charge transfer salts, which reveals three packing motifs between neighboring TCNQs: one with a zero longitudinal offset and an approximate 1 A transversal offset, another with an approximate 2 A longitudinal offset and zero transversal offset, and the third with a relatively long sigma-bond in the length of r = 1.6-1.7 A connecting two TCNQ fragments. Along with the statistical analysis of the crystal structures, we also present density functional theory calculations of the total energy, covalent pi-pi bonding interaction energy, and Coulombic repulsion energy for the [TCNQ](2)(2-)pi-dimers with various packing geometries. We find that the interactions between TCNQ anion pi-radicals include contributions from intermolecular covalent pi-pi bonding interaction and local dipole repulsions, in addition to Coulombic repulsion, van der Waals and the attractive electrostatic forces between counter-cations and TCNQ anions pointed out recently by other groups for TCNE anion radicals. We describe an approximate formula for intermolecular interaction energy, E(int) = E(coul) + E(bond) + E(vdW), for systems in vacuum, while in the solid state E(coul) is compensated by the attractive electrostatic forces between counter-cations and TCNQ anions. We conclude that the crystal packing of TCNQ molecules in their charge transfer salts is predominantly determined by the intermolecular covalent pi-pi bonding term, E(bond). 相似文献
46.
Defected fullerenes in nanopeapods form bonds with the encapsulating single-walled carbon nanotubes when irradiated by an electron beam leading to changes in the guest (fullerene) and the host (nanotube). Intrinsic reaction coordinate (IRC) analysis based on B3LYP hybrid density functional theory shows that a C1-C59 defect with a single protruding C atom is initially formed from the C60(Ih) cage. The high activation energy for this step (8.37 eV (193.0 kcal/mol)), being assumed to be accessible during irradiation, is lower than that of the Stone-Wales rearrangement on the sp2 network. The binding of the defected fullerene to the nanotube is preferential, orthogonal bonds relative to the tube axis being slightly preferred. Because of the covalent bonds formed between the guest and host, the carbon network on the nanotube is locally perturbed in the vicinity of the binding site. As a result of the new bonds, bisnorcaradiene-like as well as quinonoid-like patterns appear near the binding site. These results are interpreted using orbital interaction and Clar diagram arguments. The changes in the bonding pattern on the nanotube should be significant in further functionalization of carbon nanotubes. 相似文献
47.
We develop a holographic (bottom-up) gravity model for QCD to understand the connection between the peak in the trace anomaly and the magnitude of heavy quark energy loss in a strongly-coupled plasma. The potential of the scalar field on the gravity side is constructed to reproduce some properties of QCD at finite temperature and its parameters are constrained by fitting lattice gauge theory results. The energy loss of heavy quarks (as predicted by the holographic model) is found to be strongly sensitive to the medium properties. 相似文献
48.
Reliable conformational energetics is essential in interpreting and predicting structures of molecular crystals. We provide a combined density functional theory (DFT)-structural database study, demonstrating that this combination can be used as a foundation for this purpose. A subtle problem of nitrogen pyramidalization is used as the example in antipyrines, a group of bioactive molecules. Nitrogen pyramidalization on the two adjacent sp(3) nitrogens directly affects the orientation of the methyl and phenyl substituents, which tend toward opposite sides of the heteroaromatic ring, affecting crystal packing. Accordingly, the overwhelming majority of the structures of antipyrines in the Cambridge Structural Database (CSD) are either nearly planar or have substituents on the opposite sides of the ring. Recent powder X-ray structures by Lemmerer et al. identified propyphenazone, an antipyrine, to have two substituents on the same side in an apparently sterically crowded conformation. We show that the new structure, although counterintuitive, is not an outlier on the conformational map. A distribution of the conformations of all antipyrines listed in the CSD is in good agreement with the computed conformational map. We also examine the role of the hysteretic property of the phenyl torsion in propyphenazone and its indirect effects on its overall conformation. 相似文献
49.
Unusually long bonds or short intermolecular contacts occur in the title compounds reminiscent of pancake bonding. Pancake bonding interactions seem analogous to π-stacking interactions, but they display much shorter contact distances than normally seen in van der Waals (vdW) dimers. The interpretation of these SN and SeN containing structures has been an outstanding challenge for some time. The antibonding (π*) singly occupied molecular orbital (SOMO) of the radical is the source of two-electron multicenter bonding (2e/mc). Preferred conformations thus can be traced back to SOMO-SOMO overlap. We used several computational methods to understand the nature of pancake bonding in the title compounds including four wave function methods (WFT) and a dozen density functional theories (DFT) including empirical dispersion corrections. We used experimental data and high level CCSD(T)/6-311++G(d,p) and MRPT2/6-311++G(d,p) calculations for comparison. The analysis provided the interpretation a wealth of experimental data including conformational preferences of these SN and SeN containing radical dimers leading to a better overall understanding of pancake bonding. Analysis of the various components of the inter-radical interactions showed that SOMO-SOMO bonding interaction and dispersion interaction contribute to the binding energy and neither of these interactions alone is sufficient to bind the dimer. The dimer is predicted to show weak diradical character. 相似文献
50.
Fang Fu Laxman Gurung Miklos Czaun Thomas Mathew G.K. Surya Prakash 《Tetrahedron letters》2019,60(38):151020
Poly(4-vinyl pyridine) supported bromine/iodine complexes were prepared and probed for ipso-bromination/iodination of arylboronic acids. These solid complexes with catalytic amount of additive are found to be safe and efficient reagent system for the ipso-bromination/iodination. The reaction occurs under mild conditions and tolerates various functional groups resulting in products with high selectivity and yields. 相似文献