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181.
Amatzya Y. Meyer 《Theoretical chemistry accounts》1971,22(3):271-282
Two methods are proposed for dealing with a three-membered ring which is incorporated into a large molecule. The first, an all-valence electron approach, is an iterative CNDO/2 which provides, through bond indices, self-consistent hybridizations and valency angles. The second is compatible with -electron approaches and aims at the study of conjugation and transmission of conjugation. The methods are illustrated by application to the unsubstituted cyclopropane molecule.
For Part V, see Ref. [1]. 相似文献
Zusammenfassung Es werden zwei Methoden zur Behandlung von Molekülen, die einen Dreiring enthalten, vorgeschlagen. Die eine besteht in der iterativen Anwendung des CNDO/2-Verfahrens mit selbst-konsistenten Hybridisierungen und Valenzwinkeln. Die zweite entspricht etwa einem -Elektronenverfahren und dient besonders dem Studium von Konjugationseffekten. Illustriert werden beide am Beispiel des einfachen Cyclopropan.
Résumé On propose deux méthodes pour étudier les molécules contenant une composante cyclopropanique. La première, qui tient compte de tous les électrons de valence, est une CNDO/2 itérative qui fournit — par l'intermédiaire des indices carrés de liaison — des valeurs auto-cohérentes pour l'hybridation et les angles de valence. L'autre, compatible avec les techniques -électroniques, a pour but l'étude de la conjugaison et de la transmission de conjugaison. Les méthodes sont illustrées par application au cyclopropane non-substitué.
For Part V, see Ref. [1]. 相似文献
182.
Single crystals of Sm4OCl6 and KSm2Cl5 have been obtained by metallothermic reductions of SmCl3 with lithium (in the presence of Sm2O3 or SmOCl) and potassium, respectively, at elevated temperatures in sealed tantalum containers. Sm4OCl6 (hexagonal, P63mc, Z = 2, a = 946.59(4), c = 717.88(4) pm) and KSm2Cl5 (monoclinic, P21/c, Z = 4, a = 888.06(6), b = 784.81(5), c = 1262.77(8) pm, ß = 90.085(6)°) are true divalent samarium compounds, Sm4OCl6 with remarkably short Sm2+–O2? distances (236.0, 237.6 (3x) pm) within the [Sm4O] tetrahedron. 相似文献
183.
184.
Odile Meyer Jean-Franois Hoeffler Catherine Grosdemange-Billiard Michel Rohmer 《Tetrahedron》2004,60(52):12153-12162
An optimised gram scale synthesis allows the production of 1-deoxy-d-xylulose and 1-deoxy-d-xylulose 5-phosphate with possible deuterium labelling at C-5. Such substrates are required for investigations on the mevalonate-independent 2-C-methyl-d-erythritol 4-phosphate pathway for isoprenoid biosynthesis in bacteria and chloroplasts of phototrophic eukaryotes and for the biosynthesis of vitamins B1 (thiamine diphosphate) and B6 (pyridoxol phosphate) in bacteria. 相似文献
185.
Klaus Behmel Manfred Schulze und Ulrich Annagat 《Fresenius' Journal of Analytical Chemistry》1968,241(1):1-4
Zusammenfassung Eine einfache und genaue Methode zur Bestimmung von Si-H- und Si-Si-Gruppen wird vorgeschlagen, die auf alkalischer Hydrolyse der Substanz in einem verschlossenen und evakuierten Kolben und AuswÄgen des dem entwickelten Wasserstoff entsprechenden Wasservolumens beruht. Bei H-Gehalten von 1–2% betrÄgt die Genauigkeit ± 0,03% (abs.).
Herrn Prof. Dr. E. Asmus zum 60. Geburtstag gewidmet. 相似文献
Note on the quantitative determination of Si-H- and Si-Si-groups
A simple, robust and surprisingly exact method for the quantitative determination of Si-H- or Si-Si-groups is based on alkaline hydrolysis of the Si-H- or Si-Si-containing substances in a sealed and evacuated vessel and weighing of the volume of water equivalent to the developed volume of hydrogen. The accuracy is ± 0.03% (abs.) with H contents of 1–2%.
Herrn Prof. Dr. E. Asmus zum 60. Geburtstag gewidmet. 相似文献
186.
187.
Raab V Harms K Sundermeyer J Kovacević B Maksić ZB 《The Journal of organic chemistry》2003,68(23):8790-8797
1,8-bis(dimethylethyleneguanidino)naphthalene (DMEGN), the second example of a peralkyl guanidine "proton sponge" based on the 1,8-naphthalene backbone, was prepared and fully characterized. The crystal structure analysis of monoprotonated DMEGN reveals an unsymmetrical intramolecular hydrogen bridge. A decrease in the basicity with respect to the noncyclic parent 1,8-bis(tetramethylguanidino)naphthalene was found. Nevertheless, a new proton sponge provides a new crossbar in the ladder of highly basic neutral organic compounds. A detailed theoretical study of DMEGN and related cyclic guanidines explains this surprising experimental result. Homodesmotic reactions reveal that the intramolecular hydrogen bond contributes effectively 10 kcal/mol to proton affinity of DMEGN. 相似文献
188.
Klaus van Benthem Stephan Krämer Wilfried Sigle Manfred Rühle 《Mikrochimica acta》2002,138(3-4):181-193
An understanding of the correlation between microstructures and properties of materials require the characterization of the
material on many different length scales. Often the properties depend primarily on the atomistics of defects, such as dislocations
and interfaces. The different techniques of transmission electron microscopy allow the characterization of the structure and
of the chemical composition of materials with high spatial resolution to the atomic level: high resolution transmission electron
microscopy allows the determination of the position of the columns of atoms (ions) with high accuracy. The accuracy which
can be achieved in these measurements depends not only on the instrumentation but also on the quality of the transmitted specimen
and on the scattering power of the atoms (ions) present in the analyzed column.
The chemical composition can be revealed from investigations by analytical microscopy which includes energy dispersive X-ray
spectroscopy, mainly quantitatively applied for heavy elements, and electron energy-loss spectroscopy. Furthermore, the energy-loss
near-edge structure of EELS data results in information on the local band structure of unoccupied states of the excited atoms
and, therefore, on bonding. A quantitative evaluation of convergent beam electron diffraction results in information on the
electron charge density distribution of the bulk (defect-free) material.
The different techniques are described and applied to different problems in materials science. It will be shown that nearly
atomic resolution can be achieved in high resolution electron microscopy and in analytical electron microscopy. Recent developments
in electron microscopy instrumentation will result in atomic resolution in the foreseeable future. 相似文献
189.
Structures of Charge-Perturbed or Sterically Overcrowded Molecules. 16. Tetracyanoethylene Sodium Dimethoxyethane The Single crystal structure of [(NC)2C? C(CN)2?·Na⊕(H3CO? CH2CH2? OCH3)]∞ reveals two formula units within the triclinic (P1 ) unit cell. The tetracyanoethylene radical anions are arranged along parallel double layers, which are shifted relative to each other, and in between which are interspersed the sodium counter cations and their dimethoxyethane ligands. The distances within the double layers amount to 300 pm and the ones between them to 385 pm. The six-fold coordinated Na⊕ centers are surrounded by four radical anions with contact distances Na…?N between 250 and 254 pm as well as by a twofold solvent ligand with Na…?O of 238 and 241 pm. Due to the electron transfer to the acceptor molecule, its (NC)2C-halves twist by 8° and the bond lengths of the N?C? C subunits, bent by each 3°, are shortened up to 2 pm. The structural parameters are compared to those of the analogous potassium salt [TCNE?K⊕DME], of the dianion , of the sodium salts [(NC)3C?Na⊕]∞ as well as [(NC)2C? C(CHCH)2? C(CN)2?Na⊕]∞ and, in addition, are discussed based on geometry-optimized MNDO calculations. 相似文献
190.
Vijayasarathi Nagarajan Barbara Müller Oksana Storcheva Klaus Köhler Andreas Pöppl 《Research on Chemical Intermediates》2007,33(8):705-724
Interactions and binding sites of the solvent molecules chloroform and ethanol to bis(acetylacetonate)oxovanadium(IV) (VO(acac)2) complexes in (frozen) solutions have been investigated by pulsed electron nuclear double resonance, sum peak electron spin
echo envelope modulation and hyperfine sublevel correlation spectroscopy. The experimental proton hyperfine coupling data
of coordinating solvent molecules have been interpreted using quantum chemical calculations (density functional theory). Experimental
and computed hyperfine couplings indicate that ethanol coordinates to vanadium in the equatorial plane of VO(acac)2 and chloroform interacts via hydrogen bonding to oxygens of the acac ligands. 相似文献