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11.
Detlef Schrder Jessica Loos Helmut Schwarz Roland Thissen Jana Roithova Zdenek Herman 《International journal of mass spectrometry》2003,230(2-3):113
Singly and doubly charged C4H3+/2+ ions generated upon electron ionization (EI) of the neutral precursors 1,3-butadiene, benzene, and exo-methylene cyclopropane, respectively, are examined by sector-field mass-spectrometry. Charge stripping of the mass-selected monocations affords the corresponding dications and charge exchange of the C4H32+ dications allows for the reverse redox process. Refined analysis and additional MS/MS studies suggest that the monocations are mixtures of isomeric ions formed upon ionization, whereas only a single type of dication seems to be formed. As an average of energy-resolved measurements, a vertical ionization energy of IEv(C4H3+)=16.5±0.4 eV is derived. In addition to the experimental work, density functional theory is used for a computational exploration of the mono- and dicationic species. The best theoretical estimates are IEa(C4H3+)=16.33 eV and IEv(C4H3+)=16.49 eV for the most stable isomer H2C=C---CCH+. Combination of the experimental and theoretical findings leads to the conclusion that the diacetylene cation C4H2+ has indeed a positive proton affinity of PA(C4H2+)=1.50±0.42 eV. 相似文献
12.
Gilda H. Loew Zelek S. Herman Michael C. Zerner 《International journal of quantum chemistry》1980,18(2):481-492
The optical spectrum of a model oxyheme complex has been calculated using a new intermediate neglect of differential overlap (INDO-SCF-CI ) method that allows for the inclusion of configuration interaction and transition metals. In addition to the porphyrin π→π* transitions common to all heme proteins, four weak x,y polarized transitions observed only in oxyheme complexes have been calculated and assigned to excitations involving the lowest-empty highly delocalized (Oπ, dπ) orbital. Two broad z-polarized bands observed in the single-crystal polarized absorption spectra of oxymyoglobin and hemoglobin have also been calculated. Controversy exists over the assignment of these transitions and, in particular, over the extent of involvement of the oxygen ligand. Our calculations assign the weaker near-IR visible band mainly to the d σ dπ→ dπ* excitations and the more intense UV band mainly to a2u → dσ* excitations. While significant participation (25%) of the highly delocalized (Oπ, dπ) virtual orbital is also found, these z-polarized transitions need not be totally unique to oxyheme complexes, in keeping with experimental observation. 相似文献
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M. B. Freiler M. C. Shih S. Kim M. Levy I. P. Herman R. Scarmozzino R. M. Osgood Jr. 《Applied Physics A: Materials Science & Processing》1996,63(2):143-151
We present a study of pattern-transfer and etch-induced damage in photon-induced cryoetching. Features with effective radii as small as 100 nm have been formed in both bulk and layered GaAs/AlGaAs materials. A measurement of the photoluminescence of etch-defined deep- submicrometer structures material suggests that this form of etching results in minimal process-induced damage. Modeling of the luminescence vs feature size for these features shows that the luminescence is limited only by carrier diffusion and non-radiative surface recombination. 相似文献
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van Swieten PF Leeuwenburgh MA Kessler BM Overkleeft HS 《Organic & biomolecular chemistry》2005,3(1):20-27
The chemical labeling of biomolecules continues to be an important tool for the study of their function and cellular fate. Attention is increasingly focused on labeling of biomolecules in living cells, since cell lysis introduces many artefacts. In addition, with the advances in biocompatible synthetic organic chemistry, a whole new field of opportunity has opened up, affording high diversity in the nature of the label as well as a choice of ligation reactions. In recent years, several different two-step labeling strategies have emerged. These rely on the introduction of a bioorthogonal attachment site into a biomolecule, then ligation of a reporter molecule to this site using bioorthogonal organic chemistry. This Perspective focuses on these techniques, their implications and future directions. 相似文献
18.
Silver(I) and N,N'-bis(2-hydroxyethyl)dithiooxamide (H2X) in acidic solutions, form a series of water-soluble polynuclear complexes. These complexes can be represented by two general formulae: H2qAgpXq and H2q-1AgpXq with q=1,2,3 and p=q, q-1. 相似文献
19.
Summary Procedures were developed for the preparation of the 2-, 3-, 4-, and 6-monosubstituted chloro and bromo 8-quinolinols which afforded greater yields and/or reduced the number of steps in the preparation. 100 MHz1H-NMR spectra for the 12 possible monochloro and monobromo analogues are given.
Verbesserte Synthese von Monochlor- und Monobrom-8-chinolinolen
Zusammenfassung Es wurden Verfahren entwickelt, um 2-, 3-, 4- und 6-Chlor bzw. -Brom-8-chinolinole in besseren Ausbeuten und/oder bei reduzierter Anzahl von Synthesestufen herzustellen. Die1H-NMR-Spektren der 12 möglichen Monochlor- und Monobromverbindungen werden angegeben.相似文献
20.
Herman MF 《The journal of physical chemistry. A》2005,109(41):9196-9205
The derivation of a semiclassical surface hopping procedure from a formally exact solution of the Schrodinger equation is discussed. The fact that the derivation proceeds from an exact solution guarantees that all phase terms are completely and accurately included. Numerical evidence shows the method to be highly accurate. A Monte Carlo implementation of this method is considered, and recent work to significantly improve the statistical accuracy of the Monte Carlo approach is discussed. 相似文献