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91.
James O. Jensen 《Journal of Molecular Structure》2004,686(1-3):165-172
The normal mode frequencies and corresponding vibrational assignments of phosphirane in are examined theoretically using the GAUSSIAN 98 set of quantum chemistry codes. All normal modes were successfully assigned to one of nine types of motion (C–C stretch, P–C stretch C–H stretch, P–H stretch, CH2 scissors, CH2 wag, CH2 rock, CH2 twist, and P–H wag) predicted by a group theoretical analysis. Comparing the vibrational frequencies with IR and Raman spectra available in the literature, a set of scaling factors are derived. Predicted infrared and Raman intensities are reported. 相似文献
92.
Giesemann A 《Rapid communications in mass spectrometry : RCM》2005,19(11):1373-1380
FACE (Free Air Carbon dioxide Enrichment) has been used since 1999 to evaluate the effects of future atmospheric CO(2) concentrations on an arable crop agroecosystem. The experiment conducted at the Institute of Agroecology at the Federal Research Centre in Braunschweig consists of a typical local crop rotation of winter barley, a cover crop, sugar beet and winter wheat. The atmospheric CO2 concentration of ambient air is about 375 ppm with a delta13C value of -7 to -9 per thousand, and 550 ppm (delta13C value = -20.2 per thousand) during daylight hours in the rings fumigated with additional CO2. Thus, the surplus C can be traced in the agricultural system. Over the course of the first experimental period (3-year crop rotation period), the C-isotopic composition and the C concentration in soil were monitored monthly. Plant samples were analysed according to the relevant developmental stages of the crop under cultivation. A 13C depletion was observed in plant parts, as well as in soil samples from the FACE rings under CO2 enrichment, indicating that labelled C has reached both respective ecosystem compartments. Albeit farming management practice (especially ploughing) leads to a mixing of 'old' and 'new' C compounds throughout all soil horizons down to the end of the ploughing layer and resulted in a heterogeneous distribution of newly formed C compounds in the soil, isotope analysis of soil C reflected where the surplus C went. 相似文献
93.
Rasmussen T Jensen JF Ostergaard N Tanner D Ziegler T Norrby PO 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(1):177-184
The selectivity-determining step in enantioselective copper-catalyzed cyclopropanation with diazo compounds has been studied by experimental and computational methods. The addition of the very reactive metallacarbene intermediate in an early transition state to the substrate alkene is concerted but strongly asynchronous, with substantial cationic character on one alkene carbon in the neighborhood of the transition state. Evidence from isotope effects and Hammett studies supports the nature of the transition state. Formation of a metallacyclobutane intermediate by a [2+2] addition is kinetically disfavored. Ligand-substrate interactions influencing the enantio- and diastereoselectivity have been identified, and the preferred orientation of the alkene substrate during the addition is suggested. 相似文献
94.
Dash AK Jensen TR Stern CL Marks TJ 《Journal of the American Chemical Society》2004,126(39):12528-12540
Single-site polymerization catalysts generated in situ via activation of Cp*MMe(3) (Cp* = C(5)Me(5); M = Ti, Zr), (CGC)MMe(2) (CGC = C(5)Me(4)SiMe(2)NBu(t)(); M = Ti, Zr), and Cp(2)ZrMe(2) with Ph(3)C(+)B(C(6)F(5))(4)(-) catalyze alkylation of aromatic molecules (benzene, toluene) with alpha-chloronorbornene at room temperature, to regioselectively afford the 1:1 addition products exo-1-chloro-2-arylnorbornane (aryl = C(6)H(5) (1a), C(6)H(4)CH(3) (1b)) in good yields. Analogous deuterium-labeled products exo-1-chloro-2-aryl-d(n)-norbornane-7-d(1) (aryl-d(n) = C(6)D(5) (1a-d(6)), C(6)D(4)CD(3) (1b-d(8))) are obtained via catalytic arylation of alpha-chloronorbornene in either benzene-d(6) or toluene-d(8). Isolated ion-pair complexes such as (CGC)ZrMe(toluene)(+)B(C(6)F(5))(4)(-) and Cp(2)ThMe(+)B(C(6)F(5))(4)(-) also catalyze the reaction of alpha-chloronorbornene in toluene-d(8) to give 1b-d(8) in good yields, respectively. Small quantities of the corresponding bis(1-chloronorbornyl)aromatics 2 are also obtained from preparative-scale reactions. These reactions exhibit turnover frequencies exceeding 120 h(-1) (for the Cp*TiMe(3)/Ph(3)C(+)B(C(6)F(5))(4)(-)-catalyzed system), and chlorine-free products are not observed. Compounds 1 and 2 were characterized by (1)H, (2)H, (13)C, and 2D NMR, GC-MS, and elemental analysis. The aryl group exo-stereochemistry in 1a and 1b is established using (1)H-(1)H COSY, (1)H-(13)C HMBC, and (1)H-(1)H NOESY NMR, and is further corroborated by X-ray analysis of the product 1,4-bis(exo-1-chloro-2-norbornyl)benzene (2a). Control experiments and reactivity studies on each component step suggest a mechanism involving participitation of the metal electrophiles in the catalytic cycle. 相似文献
95.
The vibrational frequencies and corresponding normal mode assignments of urazole are examined theoretically using the Gaussian98 set of quantum chemistry codes. All normal modes were successfully assigned to one of eight types of motion (N--H stretch, C=O stretch, C--N stretch, N--N stretch, N--H bend, C=O bend, N--C--N bend, ring torsion) utilizing the C2 symmetry of the molecule. The molecular orbitals of urazole are examined. The simultaneous double inversion of the amine groups in urazole is also examined. 相似文献
96.
Jensen JO 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2004,60(11):2561-2566
The normal mode frequencies and corresponding vibrational assignments of Triethynylmethylstannane (SnCH(3)(CCH)(3)) are examined theoretically using the Gaussian 98 set of quantum chemistry codes. Each of the vibrational modes was assigned to one of nine types of motion predicted by a group theoretical analysis (Sn-C stretch, C[triple bond]C stretch, C-H stretch, C[triple bond]C-H bend, Sn-C[triple bond]C bend, C-Sn-C bend, H-C-H bend, CH(3) wag, and CH(3) twist) utilizing the C(3v) symmetry of the molecule. A set of uniform scaling factors was derived for each type of motion. Predicted infrared and Raman intensities are reported. 相似文献
97.
98.
99.
A. Płochocki K. Rykaczewski T. Batsch J. Szerypo J. Żylicz R. Barden O. Klepper E. Roeckl D. Schardt H. Gabelmann P. Hill H. Ravn T. Thorsteinsen I. S. Grant H. Grawe P. Manakos L. D. Skouras 《Zeitschrift für Physik A Hadrons and Nuclei》1992,342(1):43-51
For the first time, detailed decay-spectroscopic investigations were performed for the very neutron-deficientN=50 nuclide98Cd. The98Cd activity was produced in spallation reactions between 600 MeV protons and a natural tin target, yielding a98Cd beam intensity of 10 to 60 atoms/s at the collector of the ISOLDE massseparator. By means of-ray and conversion-electron spectroscopy, 19 transitions were found to follow the +/EC decay98Cd98Ag. The transitions at 61 and 107 keV were shown to beM1(+E2) andE2, respectively, and the98Cd half-life was measured as 9.2±0.3 s. TheQ
EC value of98Cd is determined semiempirically and is compared to model predictions together with the measuredQ
EC values of the neighbouring cadmium isotopes100,102Cd and theN=50 isotones92Mo,94Ru, and96Pd, taken from the literature. The newly established decay scheme of98Cd includes 9 excited states of98Ag. Four states at 1691, 1861, 2164, and 2544 keV are directly fed by 0+ 1+ Gamow-Teller beta transitions with a summed strength of 3.5
–0.7
+0.8
. This value corresponds to 25±5% of the strength predicted for the GT transformation of a g9/2 proton (in98Cd) into a g7/2 neutron (in98Ag) by the extreme single-particle shell model. The GT-strength splitting and quenching, observed for98Cd, are compared with the corresponding data for lighter even-even N=50 isotones, and are discussed with reference to the predictions of more sophisticated nuclear models. We find that only in some cases it is possible to explain qualitatively the observed GT strength distribution and its total magnitude without renormalizing the free-neutron value of the axial-vector coupling constant.Dedicated to Prof. P. Armbruster on the occasion of his 60th birthday 相似文献
100.