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31.
Venkatesh Vasudevan David F. Davidson Ronald K. Hanson Craig T. Bowman David M. Golden 《Proceedings of the Combustion Institute》2007,31(1):175-183
The two-channel thermal decomposition of formaldehyde [CH2O], (1a) CH2O + Ar → HCO + H + Ar, and (1b) CH2O + Ar → H2 + CO + Ar, was studied in shock tube experiments in the 2258-2687 K temperature range, at an average total pressure of 1.6 atm. OH radicals, generated on shock heating trioxane-O2-Ar mixtures, were monitored behind the reflected shock front using narrow-linewidth laser absorption. 1,3,5 trioxane [C3H6O3] was used as the CH2O precursor in the current experiments. H-atoms formed upon CH2O and HCO decomposition rapidly react with O2 to produce OH via H + O2 → O + OH. The recorded OH time-histories show dominant sensitivity to the formaldehyde decomposition pathways. The second-order reaction rate coefficients were inferred by matching measured and modeled OH profiles behind the reflected shock. Two-parameter fits for k1a and k1b, applicable in this temperature range, are:
32.
M. K. Bowman M. C. Thurnauer J. R. Norris S. A. Dikanov V. I. Gulin A. M. Tyryshkin R. I. Samoilova Yu. D. Tsvetkov 《Applied magnetic resonance》1992,3(2):353-368
The anion and cation radicals of vitamin K1 and its analog menadione were characterized using the magnetic resonance techniques of Electron Nuclear Double Resonance (ENDOR), Electron Spin Echo Envelope Modulation (ESEEM), and Electron Paramagnetic Resonance (EPR) at X-band and 2 mm-band. Theg-factor anisotropy of the radicals at 2 mm-band allow them to be distinguished from each other in the solid state. Theg-factor matrix of the radical anion of vitamin K1 is virtually identical with that reported for the reduced A1 acceptor in green plant photosystem I thus demonstrating that reduced A1 is the anion radical of vitamin K1. 相似文献
33.
Kodibagkar VD Browning CD Tang X Wu Y Bowman RC Conradi MS 《Solid state nuclear magnetic resonance》2003,24(4):254-262
Powders of three hexagonal metal-hydrides or -deuterides are found to align in 4.4–8.3 T magnetic fields used for NMR. The field-alignment is unexpected, since all three systems have very small susceptibilities, as demonstrated by sharp NMR lines. The extent of alignment runs from nearly complete to barely detectable in ZrBe2(H,D)x, LuD3, and YD3, respectively. The preferred alignment direction in ZrBe2(H,D)x is with the crystallites’ c-axis perpendicular to B, while the c-axis and B tend to be parallel in LuD3 and YD3. The susceptibilities χ|| and χ are determined from bulk magnetization measurements in aligned ZrBe2H1.4 powder. The alignment must be considered for proper analysis of NMR spectra in these and related materials. 相似文献
34.
Bowman A Allix M Pelloquin D Rosseinsky MJ 《Journal of the American Chemical Society》2006,128(39):12606-12607
The n = 3 Ruddlesden-Popper phase Sr3LaFe1.5Co1.5O10+/-delta is capable of sustaining O contents as low as O7.5 with a mean metal oxidation state of +2 and three coordination at the central site in the trilayer of originally octahedral transition metal sites. The shortening of the axial bonds to the flanking octahedral layers stabilizes the low oxidation state and consequent unusual low coordination number of the Fe2+ and Co2+ cations within the extended structure. 相似文献
35.
We review the photodissociation dynamics of formaldehyde with an emphasis on recent calculations that make use of a global ab initio-based potential energy surface for the S(0) state. These calculations together with recent experiments reveal striking departures from conventional transition state theory for the formation of the molecular products H(2) + CO. The evidence for this departure is reviewed in detail by examining properties of the new potential surface and results of quasiclassical trajectory dynamics calculations using this surface. We also review very recent work on the dynamics governing the formation of radical products, H + HCO. These products can be formed on the T(1) surface as well as the S(0) one, and we present some results contrasting the dynamics on these two surfaces. This work makes use of a new semi-global ab initio-based T(1) potential energy surface. 相似文献
36.
Smith SD Hamersky MW Bowman MK Rasmussen KØ Spontak RJ 《Langmuir : the ACS journal of surfaces and colloids》2006,22(15):6465-6468
The conditions signaling the formation of bidisperse brushes in ordered block copolymers are investigated as an A(2) block is progressively grown onto an A(1)B diblock copolymer to form a series of molecularly asymmetric, isomorphic A(1)BA(2) triblock copolymers. Small-angle scattering and self-consistent field theory confirm that the microphase-ordered period decreases when the A(2) block is short relative to the A(1) block, but then increases as A(1)+A(2) bidisperse brushes develop. The mechanical properties systematically follow the spatial distribution of the A(2) block. 相似文献
37.
Paul F. Reigler Jeff Larson Lyle Bowman 《Journal of polymer science. Part A, Polymer chemistry》1981,19(12):3247-3255
The thermal and/or catalytic degradation of chloride-containing polymers causes dehydrohalogenation which produces hydrochloric acid. A nonaqueous method has been developed for the termination of hydrochloric acid. The sample is dissolved in tetrahydrofuran and titrated potentiometrically with a standard tetrabutylammonium hydroxide solution in a 7.5% (V/V) aqueous tetrahydrofuran solution with a combination glass-calomel electrode. The method has a relative precision of ±3.7% at the 95% confidence limit and a sensitivity of 25 ppm HCI. 相似文献
38.
We report an analytical ab initio three degrees of freedom (3D) spin-orbit-correction surface for the entrance channel of the F + methane reaction obtained by fitting the differences between the spin-orbit (SO) and non-relativistic electronic ground state energies computed at the MRCI+Q/aug-cc-pVTZ level of theory. The 3D model surface is given in terms of the distance, R(C-F), and relative orientation, Euler angles ? and θ, of the reactants treating CH(4) as a rigid rotor. The full-dimensional (12D) "hybrid" SO-corrected potential energy surface (PES) is obtained from the 3D SO-correction surface and a 12D non-SO PES. The SO interaction has a significant effect in the entrance-channel van der Waals region, whereas the effect on the energy at the early saddle point is only ~5% of that at the reactant asymptote; thus, the SO correction increases the barrier height by ~122 cm(-1). The 12D quasiclassical trajectory calculations for the F + CH(4) and F + CHD(3) reactions show that the SO effects decrease the cross sections by a factor of 2-4 at low collision energies and the effects are less significant as the collision energy increases. The inclusion of the SO correction in the PES does not change the product state distributions. 相似文献
39.
John D. Mertens Katharina Kohse-Hinghaus Ronald K. Hanson Craig T. Bowman 《国际化学动力学杂志》1991,23(8):655-668
The reaction of atomic hydrogen with isocyanic acid (HNCO) to produce the amidogen radical (NH2) and carbon monoxide, has been studied in shock-heated mixtures of HNCO dilute in argon. Time-histories of the ground-state NH2 radical were measured behind reflected shock waves using cw, narrowlinewidth laser absorption at 597 nm, and HNCO time-histories were measured using infrared emission from the fundamental v2-band of HNCO near 5 μm. The second-order rate coefficient of reaction (2(a)) was determined to be: cm3 mol?1 s?1, where f and F define the lower and upper uncertainty limits, respectively. An upper limit on the rate coefficient of was determined to be: 相似文献
40.
W. Russell Bowman Anthony J. Fletcher Peter J. Lovell Elena Hernández López Graeme B.S. Potts 《Tetrahedron》2007,63(1):191-203
Amides have been successfully used as precursors of imidoyl radicals for radical cyclisation. The amides have been converted to imidoyl selanides via reaction with phosgene to yield imidoyl chlorides followed by reaction with potassium phenylselanide. Imidoyl selanides were reacted with tributyltin hydride (Bu3SnH) as the radical mediator with triethylborane or AIBN as initiators to yield imidoyl radicals for cyclisation reactions. Imidoyl radicals have been cyclised onto alkenes to yield 2,3-substituted-indoles and -quinolines and also onto pyrroles and indoles to give bi- and tricyclic heteroarenes. 相似文献