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81.
P.J. Bussey C. Raine J.G. Rutherglen P.S.L. Booth L.J. Carroll G.R. Court P.R. Daniel A.W. Edwards R. Gamet C.J. Hardwick P.J. Hayman J.R. Holt J.N. Jackson J.H. Norem W.H. Range F.H. Combley W. Galbraith V.H. Rajaratnam C. Sutton 《Nuclear Physics B》1979,154(2):205-225
Measurements have been made of the polarisation parameters Σ, T and P for the process γp → π+n in the photon energy range 520–2250 MeV at c.m. angles between 30° and 120°. These data were obtained in a double polarisation experiment, using the polarised photon beam from the Daresbury electron synchrotron incident on a polarised proton target. The data are compared with predictions from current theoretical analyses. 相似文献
82.
R. A. McD. Galbraith 《Experiments in fluids》1985,3(5):253-256
The paper presents the results of wind tunnel tests of a GU25-5(11)8 aerofoil section over the Reynolds number range, 50,000 to 610,000. For the particular test conditions, the aerofoil exhibits severe degradation of performance below Re = 300,000; a phenomenon which is known to be quite general. This particular aerofoil section has been used for the canards of microlights where low Reynolds numbers are common. 相似文献
83.
Galbraith JM Schreiner PR Harris N Wei W Wittkopp A Shaik S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2000,6(8):1446-1454
The Bergman cyclization of (Z)-hex-3-ene-1,5-diynes (1, enediynes), which produces pharmacologically important DNA-cleaving biradicals (1,4-benzyne, 2), was studied by using Hartree-Fock (HF) and density-functional theory (DFT) based valence bond (VB) methods (VB-HF and VB-DFT, respectively). We found that only three VB configurations are needed to arrive at results not too far from complete active space [CASSCF(6 x 6)] computations, while the quality of VB-DTF utilizing the same three configurations improves upon CASSCF(6 x 6) analogous to CASPT2. The dominant VB configuration in 1 contributes little to 2, while the most important biradical configuration in 2 plays a negligible role in 1. The avoided crossing of the energy curves of these two configurations along the reaction coordinate leads to the transition state (TS). As a consequence of the shape and position of the crossing section, the changes in geometry and in the electronic wavefunction along the reaction coordinate are non-synchronous; the TS is geometrically approximately 80% product-like and electronically approximately 70% reactant-like. While the pi resonance in the TS is very small, it is large (64.4 kcal mol(-1)) for 2 (cf. benzene=61.5 kcal mol(-1)). As a consequence, substituents operating on the sigma electrons should be much more effective in changing the Bergman reaction cyclization barrier. Furthermore, additional sigma resonance in 2 results in unusually high values for the nucleus-independent chemical shift (NICS, a direct measure for aromaticity). Similarly, the high NICS value of the TS is due mostly to sigma resonance to which the NICS procedure is relatively sensitive. 相似文献
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(8/8)CASSCF and (8/8)CASPT2 calculations have been performed in order to investigate the potential surface for the ring expansion of the (1)A(2) state of phenylphosphinidene (1c) to 1-phospha-1,2,4,6-cycloheptatetraene (3c). Unlike the comparable ring expansion of the (1)A(2) state of phenylnitrene (1b) to 1-aza-1,2,4,6-cycloheptatetraene (3b), ring expansion of 1c to 3c is computed to be quite endothermic. Nevertheless, cyclization of 1c, to form the bicyclic intermediate 2c in the ring expansion reaction, is computed to be only slightly more endothermic than the comparable cyclization reaction of 1b to 2b. The origins of these differences between the ring expansion reactions of 1b and 1c have been elucidated through the calculation of the energies of relevant isodesmic reactions. 相似文献
88.
Gramicidin is an excellent model system for studying the passage of ions through biological membranes. The conformation of gramicidin is well defined in many different solvent and lipid systems, as are its conductance and spectroscopic properties. It is a polymorphic molecule that can adopt two different types of structure, the double helical "pore" and the helical dimer "channel". This study investigated the influence of the acyl chain length of membrane phospholipids on the conformations adopted by gramicidin. We used circular dichroism spectroscopy to examine the conformational equilibrium between the pore and channel forms in small unilamellar vesicles of phosphatidylcholine with acyl chain lengths of 18, 20 and 22 carbons. Our results show that in C18 and C20 lipids almost all the gramicidin is in the channel form, while in the longer C22 lipids the equilibrium shifts in favour of pore conformations, such that they form up to 43% of the total population. This change is attributed to the ability of the double helical conformation to tolerate more hydrophobic mismatch than the helical dimer, perhaps due to the greater number of stabilising intermolecular hydrogen bonds. 相似文献
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