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31.
The intensities of the vibrationally induced bands in the S1---S0 emission and absorption spectra of pyrene-h10 and -d10 are measured and analysed. Several new expressions are reported which relate the deuterium effect and emission—absorption asymmetry of induced spectra to the vibronic coupling mechanism. 相似文献
32.
Isothermal adsorption of Ar on single walled carbon nanotubes (SWNTs) has been studied at 77 and 87 K. The SWNTs have been grown by laser vaporization of a graphite pellet containing 0.6% (atomic) Ni/Co catalyst. The nanotubes have been prepared for argon adsorption measurements by prolonged outgassing of as-grown material in a vacuum at room temperature (295 K), at elevated temperatures of up to 475 K, and by oxidization for 2 h in dry air at 470 K. Formation of two condensed phases of Ar in the interior of SWNTs has been observed at 77 K. The low-density phase is formed at 155(5) microTorr, while the high-density phase, at 120(5) microTorr. At 87 K, only a single phase has been observed at 185(5) microTorr. Condensation at both 77 and 87 K appears to be the first-order phase transition. Onset of the quasi-one-dimensional linear (one-channel) phase and the quasi-two-dimensional monolayer (six-channel) phase formation on the external surface of bundles has been observed at 77 K near 0.0017 and 0.8 Torr, respectively, and at 87 K near 0.018 and 5 Torr, respectively. Isosteric heats of adsorption for the one-channel phase, the first external layer, and the second external layer have been determined to be equal to 137, 107, and 70 meV, respectively. 相似文献
33.
In the area of peptide and nucleic acid chemistry and biology, high-throughput synthesis has played an important role in providing useful small-molecule-based chemical probes in understanding the structure and function relationships. The past several years, there has been a constant rise in interest toward understanding the biological roles and functions of another important class of biomolecules, i.e., carbohydrates and carbohydrate conjugates. Although at early stages, in recent years, several groups have developed high-throughput synthetic methods to obtain complex carbohydrates or carbohydrate-like small-molecules. The present review article summarizes some of these developments. 相似文献
34.
Wang W Low PJ Carty AJ Sappa E Gervasio G Mealli C Ienco A Perez-Carreño E 《Inorganic chemistry》2000,39(5):998-1005
The compound [Ru3(CO)9[mu-P(NPri2)2]3][Ru6(CO)15(mu 6-C)[mu-P(NPri2)2]] (1), obtained via the addition of PCl(NPri2)2 to K2[Ru4(CO)13], crystallizes in the monoclinic space group P2l/c with a = 15.537(8) A, b = 36.151(16) A, c = 19.407(5) A, beta = 91.14(2) degrees, Z = 4, and R = 0.069 for 8006 observed reflections. The unit cell is unusual in that it contains both a typical octahedral Ru6 cluster anion (1a), featuring an encapsulated carbide, and a symmetrical phosphido bridge, in addition to a 50-electron trinuclear cluster cation [Ru3(CO)9[mu-P(NPri2)2]3]+ (1c). The latter, with approximate D3h symmetry, exhibits long Ru-Ru distances (> or = 3.15 A). Among the family of clusters with M3(mu-PR2)3 cores and different numbers of both electrons (TEC) and terminal ligands (LxLyLz), 1c is unique in that it is a 333 stereotype with 50 valence electrons. MO calculations permit us to predict the existence of redox congeners of 1c clusters and related 48e Re3 clusters. This work also presents a summary of the relationships between the electronic and the geometric structures for all known M3LxLyLz(mu-PR2)3 species. The basic stereochemical features are influenced by the total-electron count and, hence, by the degree of M-M bonding, as well as the remarkable flexibility of the phosphido bridging ligands. The mu-PR2 ligands need not necessarily lie in the M3 plane, and a wide range of M-P-M angles (as small as 72 degrees or as large as 133 degrees) have been observed. 相似文献
35.
Proton NMR shielding constants and chemical shifts for hydrogen guests in small and large cages of structure II clathrates are calculated using density-functional theory and the gauge-invariant atomic-orbital method. Shielding constants are calculated at the B3LYP level with the 6-311++G(d,p) basis set. The calculated chemical shifts are corrected with a linear regression to reproduce the experimental chemical shifts of a set of standard molecules. The calculated chemical shifts of single hydrogen molecules in the small and large structure II cages are 4.94 and 4.84 ppm, respectively, which show that within the error range of the method the H2 guest molecules in the small and large cages cannot be distinguished. Chemical shifts are also calculated for double occupancy of the hydrogen guests in small cages, and double, triple, and quadruple occupancy in large cages. Multiple occupancy changes the chemical shift of the hydrogen guests by approximately 0.2 ppm. The relative effects of other guest molecules and the cage on the chemical shift are studied for the cages with multiple occupancies. 相似文献
36.
The ν3 fundamental band (CO stretch) of HDCO at 1724 cm?1 has been studied using both conventional infrared absorption and CO laser Stark spectroscopy. In addition to the excited-state (v3 = 1) rotational constants, improved constants for the ground state of HDCO have been obtained by combining previous microwave data with some infrared combination differences. The following constants were determined:
Constant | Ground state | state | Units |
1724.267 | cm?1 | ||
198 119.75 | 198 210.4 | MHz | |
34 910.646 | 34 676.6 | MHz | |
29 561.488 | 29 331.3 | MHz | |
2.3302 | 2.3486 | D | |
0.195 | 0.190 | D |