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251.
Evans WJ Perotti JM Brady JC Ziller JW 《Journal of the American Chemical Society》2003,125(17):5204-5212
The tethered olefin cyclopentadienyl ligand, [(C(5)Me(4))SiMe(2)(CH(2)CH=CH(2))](-), forms unsolvated metallocenes, [(C(5)Me(4))SiMe(2)(CH(2)CH=CH(2))](2)Ln (Ln = Sm, 1; Eu, 2; Yb, 3), from [(C(5)Me(4))SiMe(2)(CH(2)CH=CH(2))]K and LnI(2)(THF)(2) in good yield. Each complex in the solid state has both tethered olefins oriented toward the Ln metal center with the Ln-C(terminal alkene carbon) distances 0.2-0.3 A shorter than the Ln-C(internal alkene carbon) distances. The olefinic C-C bond distances in 2 and 3, 1.328(4) and 1.328(5) A, respectively, are normal. Like its permethyl analogue, (C(5)Me(5))(2)Sm(THF)(2), complex 1 reductively couples CO(2) to form the oxalate-bridged dimer [[(C(5)Me(4))SiMe(2)(CH(2)CH=CH(2))](2)Sm](2)(mu-eta(2):eta(2)-O(2)CCO(2)), 4, in which the tethered olefins are noninteracting substituents. Complex 1 reacts with AgBPh(4) to form an unsolvated cation that has the option of coordinating [BPh(4)](-) or a pendant olefin, a competition common in olefin polymerization catalysis. The structure of [[(C(5)Me(4))SiMe(2)(CH(2)CH=CH(2))](2)Sm][BPh(4)], 5, shows that both pendant olefins are located near samarium rather than the [BPh(4)](-) counterion. 相似文献
252.
Ferro-Luzzi M Bouwhuis M Passchier E Zhou Z Alarcon R Anghinolfi M van Bommel R Botto T van den Brand JF Buchholz M Bulten HJ Choi S Comfort J Dolfini S Ent R Gaulard C Higinbotham D de Jager CW van Klaveren EP Konstantinov E Lang J de Lange DJ Miller MA Nikolenko D Nooren GJ Papadakis N Passchier I Poolman HR Popov SG Rachek I Ripani M Six E Steijger JJ Taiuti M Unal O Vodanis N de Vries H 《Physical review letters》1996,77(13):2630-2633
253.
254.
Hansen AK Almagri AF Craig D Den Hartog DJ Hegna CC Prager SC Sarff JS 《Physical review letters》2000,85(16):3408-3411
A cause of observed anomalous plasma momentum transport in a reversed-field pinch is determined experimentally. Magnetohydrodynamic theory predicts that nonlinear interactions involving triplets of tearing modes produce internal torques that redistribute momentum. Evidence for the nonlinear torque is acquired by detecting the correlation of momentum redistribution with the mode triplets, with the elimination of one of the modes in the triplet, and with the external driving of one of the modes. 相似文献
255.
Lanier NE Craig D Anderson JK Biewer TM Chapman BE Den Hartog DJ Forest CB Prager SC Brower DL Jiang Y 《Physical review letters》2000,84(10):2120-2123
Contrary to what has been observed thus far collision-induced light scattering (CILS) can be completely polarized. This exceptional behavior characterizes the very far wing of the binary CILS spectrum by gaseous helium. This conclusion is drawn from an experimental study of the depolarization ratio of He (2) in a much extended, previously unexplored, spectral domain. Our analysis shows that this property, unique thus far, is mainly due to an almost perfect cancellation between polarization and exchange pair polarizability contributions to the depolarized spectrum, taking place at internuclear distances shorter than the atomic diameter. 相似文献
256.
Chung P Ajitanand NN Alexander JM Anderson M Best D Brady FP Case T Caskey W Cebra D Chance JL Cole B Crowe K Das A Draper JE Gilkes ML Gushue S Heffner M Hirsch AS Hjort EL Huo L Justice M Kaplan M Keane D Kintner JC Klay J Krofcheck D 《Physical review letters》2000,85(5):940-943
We have measured the sideward flow of neutral strange ( K(0)(s)) mesons in 6A GeV Au+Au collisions. A prominent antiflow signal is observed for an impact parameter range ( b less, similar7 fm) which spans central and midcentral events. Since the K(0)(s) scattering cross section is relatively small in nuclear matter, this observation suggests that the in-medium kaon vector potential plays an important role in high density nuclear matter. 相似文献
257.
Suppose that a consistent one-step numerical method of orderr is applied to a smooth system of ordinary differential equations.Given any integer m 1, the method may be shown to be of orderr + m as an approximation to a certain modified equation. Ifthe method and the system have a particular qualitative propertythen it is important to determine whether the modified equationsinherit this property. In this article, a technique is introducedfor proving that the modified equations inherit qualitativeproperties from the method and the underlying system. The techniqueuses a straightforward contradiction argument applicable toarbitrary one-step methods and does not rely on the detailedstructure of associated power series expansions. Hence the conclusionsapply, but are not restricted, to the case of Runge-Kutte methods.The new approach unifies and extends results of this type thathave been derived by other means: results are presented forintegral preservation, reversibility, inheritance of fixed points.Hamiltonian problems and volume preservation. The techniquealso applies when the system has an integral that the methodpreserves not exactly, but to order greater than r. Finally,a negative result is obtained by considering a gradient systemand gradient numerical method possessing a global property thatis not shared by the associated modified equations. 相似文献
258.
Henry W Coates CG Brady C Ronayne KL Matousek P Towrie M Botchway SW Parker AW Vos JG Browne WR McGarvey JJ 《The journal of physical chemistry. A》2008,112(20):4537-4544
The early picosecond time scale excited-state dynamics of the paradigm tris(2,2'-bipyridyl)Ruthenium(II) ([Ru(bpy)(3)](2+)) and related complexes have been examined by picosecond Kerr-gated time-resolved resonance Raman (ps-TR(3)) spectroscopy. The evolution of the signature Raman bands of the lowest thermally equilibrated excited (THEXI) state under two-color pump/probe conditions show that this state is not fully populated within several hundred femtoseconds as proposed previously but rather only within the first 20 ps following excitation. In addition to an emission observed within the instrument rise time (τ < 3 ps), the early picosecond dynamics are characterized by a rise in the intensity of the Raman marker bands of the THEXI-(3)MLCT state, a rise time which, within experimental uncertainty, is not influenced by either partial or complete ligand deuteriation or the presence of ligands other than bpy, as in the heteroleptic complexes [Ru(bpy)(2)(L1)](+) and [Ru(bpy)(2)(Hdcb)](+) (where H(2)dcb is 4,4'-dicarboxy-2,2'-bipyridine and L1 is 2,-(5'-phenyl-4'-[1,2,4]triazole-3'-yl)pyridine). Overall, although the results obtained in the present study are consistent with those obtained from examination of this paradigm complex on the femtosecond timescale, regarding initial formation of the vibrationally hot (3)MLCT state by ISC from the singlet Franck-Condon state, the observation that the THEXI-(3)MLCT state reaches thermal equilibration over a much longer time period than previously suggested warrants a re-examination of views concerning the rapidity with which thermal equilibration of transition metal complex excited states takes place. 相似文献
259.
Guvench O Greene SN Kamath G Brady JW Venable RM Pastor RW Mackerell AD 《Journal of computational chemistry》2008,29(15):2543-2564
We present an all-atom additive empirical force field for the hexopyranose monosaccharide form of glucose and its diastereomers allose, altrose, galactose, gulose, idose, mannose, and talose. The model is developed to be consistent with the CHARMM all-atom biomolecular force fields, and the same parameters are used for all diastereomers, including both the alpha- and beta-anomers of each monosaccharide. The force field is developed in a hierarchical manner and reproduces the gas-phase and condensed-phase properties of small-molecule model compounds corresponding to fragments of pyranose monosaccharides. The resultant parameters are transferred to the full pyranose monosaccharides, and additional parameter development is done to achieve a complete hexopyranose monosaccharide force field. Parametrization target data include vibrational frequencies, crystal geometries, solute-water interaction energies, molecular volumes, heats of vaporization, and conformational energies, including those for over 1800 monosaccharide conformations at the MP2/cc-pVTZ//MP2/6-31G(d) level of theory. Although not targeted during parametrization, free energies of aqueous solvation for the model compounds compare favorably with experimental values. Also well-reproduced are monosaccharide crystal unit cell dimensions and ring pucker, densities of concentrated aqueous glucose systems, and the thermodynamic and dynamic properties of the exocyclic torsion in dilute aqueous systems. The new parameter set expands the CHARMM additive force field to allow for simulation of heterogeneous systems that include hexopyranose monosaccharides in addition to proteins, nucleic acids, and lipids. 相似文献
260.
Linghao Zhong James F. Matthews Michael F. Crowley Tauna Rignall César Talón Joseph M. Cleary Ross C. Walker Giridhar Chukkapalli Clare McCabe Mark R. Nimlos Charles L. Brooks III Michael E. Himmel John W. Brady 《Cellulose (London, England)》2008,15(2):261-273
We describe the construction of a model complex of the cellobiohydrolase I (CBH I) cellulase from Trichoderma reesei bound to a cellulose microfibril in an aqueous environment for use in molecular dynamics (MD) simulations. Preliminary characterization
from the initial phases of an MD simulation of this complex is also described. The linker sequence between the two globular
domains was found to be quite flexible, and the oligosaccharides bound to this linker were found to prefer to be splayed like
the spokes in a wheel due to their hydration requirements. The overall conformations of the two globular domains remained
stable in the simulations, although both underwent changes in their orientations. 相似文献