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21.
Dixon FM Masar MS Doan PE Farrell JR Arnold FP Mirkin CA Incarvito CD Zakharov LN Rheingold AL 《Inorganic chemistry》2003,42(10):3245-3255
The ligand 1,4-bis[4-(diphenylphosphino)butyl]-2,3,5,6-tetramethylbenzene, 3, was used to synthesize a mononuclear Rh(II) complex [(eta(1):eta(6):eta(1)-1,4-bis[4-(diphenylphosphino)butyl]-2,3,5,6-tetramethylbenzene)Rh][PF(6)](2), 6+, in a two-legged piano-stool geometry. The structural and electronic properties of this novel complex including a single-crystal EPR analysis are reported. The complex can be cleanly interconverted with its Rh(I) form, allowing for a comparison of the structural properties and reactivity of both oxidation states. The Rh(I) form 6 reacts with CO, tert-butyl isocyanide, and acetonitrile to form a series of 15-membered mononuclear cyclophanes [(eta(1):eta(1)-1,4-bis[4-(diphenylphosphino)butyl]-2,3,5,6-tetramethylbenzene)Rh(CO)(3)][PF(6)] (8), [(eta(1):eta(1)-1,4-bis[4-(diphenylphosphino)butyl]-2,3,5,6-tetramethylbenzene)Rh(CNC(CH(3))(3))(2)][PF(6)] (10), and [(eta(1):eta(1)-1,4-bis[4-(diphenylphosphino)butyl]-2,3,5,6-tetramethylbenzene)Rh(CO)(CH(3)CN)][PF(6)] (11). The Rh(II) complex 6+ reacts with the same small molecules, but over shorter periods of time, to form the same Rh(I) products. In addition, a model two-legged piano-stool complex [(eta(1):eta(6):eta(1)-1,4-bis[3-(diphenylphosphino)propoxy]-2,3,5,6-tetramethylbenzene)Rh][B(C(6)F(5))(4)], 5, has been synthesized and characterized for comparison purposes. The solid-state structures of complexes 5, 6, 6+, and 11 are reported. Structure data for 5: triclinic; P(-)1; a = 10.1587(7) A; b = 11.5228(8) A; c = 17.2381(12) A; alpha = 96.4379(13) degrees; beta = 91.1870(12) degrees; gamma = 106.1470(13) degrees; Z = 2. 6: triclinic; P(-)1; a = 11.1934(5) A; b = 12.4807(6) A; c = 16.1771(7) A; alpha = 81.935(7) degrees; beta = 89.943(1) degrees; gamma = 78.292(1) degrees; Z = 2. 6+: monoclinic; P2(1)/n; a = 11.9371(18) A; b = 32.401(5) A; c = 12.782(2) A; beta = 102.890(3) degrees; Z = 4. 11: triclinic; P(-)1; a = 13.5476(7) A; b = 13.8306(7) A; c = 14.9948(8) A; alpha = 74.551(1) degrees; beta = 73.895(1) degrees; gamma = 66.046(1) degrees; Z = 2. 相似文献
22.
The wavefunctions and various partitions of the energy are examined for a variety of small molecules (H2, H3, H4, HeH, HeH2, He2, LiH, and BH) in order to isolate the factors crucial for bond formation. We find that a natural partition of the energy leads to the conclusion that the crucial factor is the exchange, or nonclassical, part of the kinetic energy, T
x. The change in T
xupon pushing the atoms towards one another is the dominant term in the binding energy; it is negative when the resulting molecule is stable and positive when it is unstable. We show that T
x is related to the interference kinetic energy considered by Ruedenberg.
Partially supported by a grant (GP-15423) from the National Science Foundation. This paper is based on a portion of the PhD thesis (California Institute of Technology, 1970) by CWW.
National Science Foundation Predoctoral Trainee.
Alfred P. Sloan Foundation Research Fellow.
Contribution No. 3917. 相似文献
Zusammenfassung Die Wellenfunktionen und verschiedene Zerlegungen der Energie werden für eine Reihe kleiner Moleküle untersucht (H2, H3, H4, HeH, HeH2, He2, LiH und BH), um die Faktoren zu finden, die für die Bindungsbildung ausschlaggebend sind. Die natürliche Zerlegung der Energie läßt die Folgerung zu, daß der bestimmende Faktor der Austauschanteil T x(oder nichtklassische Anteil) der kinetischen Energie ist. Die Änderung von T xbeim Zusammenführen der Atome ist der dominierende Term für die Bindungsenergie; er ist negativ, wenn das resultierende Molekül stabil ist, und positiv, falls es instabil ist. Es wird gezeigt, daß T x im Zusammenhang zum Wechselwirkungsanteil der kinetischen Energie nach Ruedenberg steht.
Partially supported by a grant (GP-15423) from the National Science Foundation. This paper is based on a portion of the PhD thesis (California Institute of Technology, 1970) by CWW.
National Science Foundation Predoctoral Trainee.
Alfred P. Sloan Foundation Research Fellow.
Contribution No. 3917. 相似文献
23.
S. L. Maxwell III 《Journal of Radioanalytical and Nuclear Chemistry》2006,270(3):651-655
Summary The measurement of radium isotopes in natural waters is important for oceanographic studies and for public health reasons.
Radium-226 (T1/2 = 1620 y) is one of the most toxic of the long-lived alpha-emitters present in the environment due to its long life and its
tendency to concentrate in bones, which increases the internal radiation dose of individuals. The analysis of 226Ra and 228Ra in natural waters can be tedious and time-consuming. Different sample preparation methods are often required to prepare
226Ra and 228Ra for separate analyses. A rapid method has been developed at the Savannah River Environmental Laboratory that effectively
separates both 226Ra and 228Ra (via 228Ac) for assay. This method uses MnO2 Resin from Eichrom Technologies (Darien, IL, USA) to preconcentrate 226Ra and 228Ra rapidly from water samples, along with 133Ba tracer. DGA Resinò (Eichrom) and Ln-Resinò (Eichrom) are employed in tandem to prepare 226Ra for assay by alpha-spectrometry and to determine 228Ra via the measurement of 228Ac by gas proportional counting. After preconcentration, the manganese dioxide is dissolved from the resin and passed through
stacked Ln-Resin-DGA Resin cartridges that remove uranium and thorium interferences and retain 228Ac on DGA Resin. The eluate that passed through this column is evaporated, redissolved in a lower acidity and passed through
Ln-Resin again to further remove interferences before performing a barium sulfate microprecipitation. The 228Ac is stripped from the resin, collected using cerium fluoride microprecipitation and counted by gas proportional counting.
By using vacuum box cartridge technology with rapid flow rates, sample preparation time is minimized. 相似文献
24.
Summary Copper phthalocyanine tetra sulfonate pottasium salt, has been found to be very useful as a screening-dye to improve methyl orange end-points.Mixtures of methyl orange and dye in varying proportions have been prepared and tested for their indicator-action. The transformation interval of the indicator is found to change as the concentration of the dye is varied in the mixture.The optimum concentration of the dye to be used with a certain amount of methyl orange is determined so as to give a mixed-indicator that functions most satisfactorily in all titrations where methyl orange is used. 相似文献
25.
The resonance frequencies of 13 polygonal vibrations plus 11 axisymmetric vibrations have been observed for a 4.0-mg sessile mercury droplet submerged in 0.10 N KCl solution. When an input voltage with suitable dc and ac components was applied between the mercury droplet and a Ag/AgCl counter electrode, the mercury droplet could be observed under a microscope to oscillate. The mechanism that drives this droplet into oscillation differs from past electrokinetic mechanisms. Basically, the oscillating input voltage causes periodic changes in the interfacial surface tension which, at specific input frequencies, induce resonant vibrations within the droplet by interacting with its expanding and contracting surface area. Because there are two cycles of surface-area variation and two cycles of surface-tension variation per cycle of droplet oscillation, the most effective driving frequency (but not the only driving frequency) is twice the frequency of the droplet oscillation. This work was performed at the Oak Ridge Y-12 Plant, Oak Ridge, Tennessee. 相似文献
26.
R. E. Beverly III 《Applied physics. B, Lasers and optics》1991,53(3):187-193
Discharge behavior of large-aperture (10–70 cm) CO2 lasers is computed using a coupled particle kinetics-equivalent circuit model. Pulsed power systems that produce a single excitation pulse are only able to satisfy the preionization, ignition, and impedance matching conditions for interelectrode gaps 40–50 cm. Double-pulse systems are required for larger gaps, not only to optimize electrical efficiency, but to avoid oscillatory behavior which can lead to arc formation during the second cycle. 相似文献
27.
R. E. Beverly III 《Optical and Quantum Electronics》1982,14(6):501-513
Onset of the dissociative-attachment instability requires that the rate coefficient for electron detachment (k
d) from negative ions be below a critical value. The predominant negative and positive ions in a CO2N2He gas-discharge plasma are known to change with time. As secondary by-products form and the predominant negative-ion species changes from CO
3
–
to NO
2
–
, a decrease ink
d occurs destabilizing the discharge. Since NO
2
–
and NO
3
–
are largely unreactive with respect to associative detachment,k
d depends in a sensitive fashion on the concentration of certain minority negative ions (O–, O
2
–
) and neutrals (CO, O, N). The sufficient conditions for the dissociative-attachment instability are much less sensitive to changes in the electron-ion and ion-ion recombination rate coefficients resulting from the ion aging process. 相似文献
28.
29.
A. Wilmer III 《International Journal of Mathematical Education in Science & Technology》2013,44(2):238-243
A method is developed in which an analytical solution is obtained for certain classes of second-order differential equations with variable coefficients. By the use of transformations and by repeated iterated integration, a desired solution is obtained. This alternative method represents a different way to acquire a solution from classic power series techniques and other approaches. It is, at times, more involved than traditional methods. 相似文献
30.