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71.
Sancho-García JC Brédas JL Beljonne D Cornil J Martínez-Alvarez R Hanack M Poulsen L Gierschner J Mack HG Egelhaaf HJ Oelkrug D 《The journal of physical chemistry. B》2005,109(11):4872-4880
Various end-substituted distyrylbenzenes have been synthesized to serve as guest molecules in inclusion compounds to promote efficient energy transport along one-dimensional channels. Their optical and photophysical properties have been characterized at both experimental and theoretical levels. All molecules display a large transition dipole moment between the ground state and lowest excited state and hence a short radiative lifetime (on the order of 1-2 ns). They also exhibit a large spectral overlap between the emission and absorption spectra, which enables efficient energy transport between molecules arranged in a head-to-tail configuration in nanochannels. Hopping rates on the order of 10(12) s(-1) are calculated at a full quantum-chemical level; this is much larger than the radiative lifetimes and opens the way for energy migration over large distances. Changes in the nature of the terminal substituents are found to modulate the optical properties weakly but to impact significantly the energy transfer rates. 相似文献
72.
[reaction: see text] The room-temperature radical addition of sodium hypophosphite to terminal alkynes produces the previously unknown 1-alkyl-1,1-bis-H-phosphinates in moderate yield. The reaction is initiated by R3B and air and proceeds under mild conditions in an open container. The bissodium salts precipitate spontaneously from the reaction mixtures, thus providing a simple purification procedure and the opportunity for multigram synthesis. The 1,1-bis-H-phosphinate products are novel precursors of the biologically important 1,1-bisphosphonates. 相似文献
73.
74.
We describe the fabrication and characterization of a free-standing silica glass membrane waveguide formed using fiber fabrication processes. The membrane has a thickness of 0.6 microm and a width of 60 microm and is many meters long. The optical attenuation is measured as 0.4 dB/m. Such attenuation outperforms that of conventional planar waveguides by several orders of magnitude. 相似文献
75.
We show, using extensive molecular dynamics simulations, that the dynamics of the electric double layer (EDL) is very much dependent on the wettability of the charged surface on which the EDL develops. For a wetting surface, the dynamics, characterized by the so-called zeta potential, is mainly controlled by the electric properties of the surface, and our work provides a clear interpretation for the traditionally introduced immobile Stern layer. In contrast, the immobile layer disappears for nonwetting surfaces, and the zeta potential deduced from electrokinetic effects is considerably amplified by the existence of a slippage at the solid substrate. 相似文献
76.
We proceed with our study of increasing self-described sequences F, beginning with 1 and defined by a functional equation
In [1] we exhibited the simple solution f (t)=Ct, for some (0,1), of the associated functional-differential equation
and we proved that provided <2/(2+d()), where
we have the asymtotic equivalence F(m)~ Cm.In the present paper we show that this last result is optimal, in the sense that the self-described sequence defined by |F–1(m)|=F(m)2, that is
for which the boundary case =2/(2+d())(=1/2) holds, does not satisfy F(m) ~ Cm. We also show that the m-th term F(m) of a sequence F for which the boundary case holds is nevertheless of asymptotic order m.Then we investigate the behaviour of self-described sequences F when lies beyond the boundary case. In [1] we established the estimates
when is the unique fixed point of a certain associated function. We were only able to prove in general that the latter holds when does not lie beyond the boundary case, however. In the present paper we prove that whenever
is the unique fixed point of this function, and in addition we obtain estimates more precise than (*). This applies for instance to the sequence defined by
that is
相似文献
77.
78.
L. Joly V. Zéninari B. Parvitte D. Weidmann D. Courtois Y. Bonetti T. Aellen M. Beck J. Faist D. Hofstetter 《Applied physics. B, Lasers and optics》2003,77(6-7):703-706
We report results of spectroscopic measurements with a continuous-wave distributed-feedback quantum-cascade laser (DFB QCL). Line intensities and self-broadening coefficients were measured in the 1 band of SO2 between 1088 and 1090 cm-1. The self-broadening coefficients in this paper confirm the typical decrease of self with increasing rotational quantum number Ka
. The line intensities determined here are smaller than those in the HITRAN 2000 database. Several lines found in this study were not present in the database. PACS 07.57.Ty; 33.20.Ea 相似文献
79.
Kerdelhué JL Langenwalter KJ Warmuth R 《Journal of the American Chemical Society》2003,125(4):973-986
Photolysis of p-tolyldiazirine (6) in the inner phase of a hemicarcerand with four butane-1,4-dioxy linker groups (5) in C(6)D(5)CD(3) at 77 K yields the 5-methylcycloheptatetraene hemicarceplex 5 circle 3b in 41% together with innermolecular reaction products resulting from an insertion of transient p-tolylcarbene (1b) into an acetal C-H or linker C-O bond of 5 and from the addition of 1b to an aryl unit of 5. The yield of incarcerated 3b increased up to 67% if 6 is photolyzed inside a hemicarcerand with deuterated spanners and butane-1,4-dioxy linker groups (d(48)-5). Hemicarceplex 5 circle 3b is not formed if the photolysis is carried out in CDCl(3). Incarcerated 3b is stable at room temperature in the absence of oxygen and is characterized by 1D and 2D NMR spectroscopy. In the presence of oxygen, 3b reacts quantitatively to yield toluene and CO(2). Upon heating solutions of d(48)-5 circle 3b in C(6)D(5)CD(3), 3b rearranges to 1b and m-tolylcarbene (18). Both tolylcarbenes immediately react with the surrounding host. From a product analysis and the measured rate constants for the thermal decomposition of d(48)-5 circle 3b in the temperature range 70-102 degrees C, the activation parameters for the 3b to 1b and 3b to 18 rearrangements are calculated (3b to 1b: DeltaG(373)++ = 27.3 +/- 1.4 kcal/mol, DeltaH(373)++ = 26.4 +/- 1.0 kcal/mol, TDeltaS(373)++ = -0.9 +/- 1.0 kcal/mol; 3b to 18: DeltaG(373)++ = 27.8 +/- 1.4 kcal/mol, DeltaH(373)++ = 19.7 +/- 1.0 kcal/mol, TDeltaS(373)++ = 8.1 +/- 1.0 kcal/mol). These values are compared with those calculated by Geise and Hadad at the B3LYP/6-311+G** level of theory (Geise, C. M.; Hadad, C. M. J. Org. Chem. 2002, 67, 2532-2540). The slightly higher inner phase activation free energy of the 3b to 18 rearrangement is explained through steric constraints imposed by the surrounding hemicarcerand on the transition state. The enthalpy-entropy compensation observed for the 3b to 18 rearrangement is discussed and interpreted as a result of a hemicarcerand and solvent reorganization along the reaction coordinate. It is taken as indirect evidence for the intermediacy of 2-methylbicyclo[4.1.0]hepta-2,4,6-triene in the 3b to 18 rearrangement. 相似文献
80.
Guillou C Beunard JL Gras E Thal C 《Angewandte Chemie (International ed. in English)》2001,40(24):4745-4746