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91.
The mechanism for abstraction of preadsorbed oxygen from CaO(100) by CO(g) to form CO2(g) is investigated by electronic structure calculations. The reaction mechanism is assumed to be the reverse of the one obtained for the decomposition of N2O(g) at CaO(100) [Surf. Sci 292 (1993) 317]. A 32 kcal/mol barrier for reaction is calculated. Adsorbed oxygen, Oads, to surface vibration frequencies in the range 840–930 cm−1 are calculated. These values are in qualitative agreement with experiment. 相似文献
92.
Infinite sequential games, in which Nature chooses a Borel winning set and reveals it to one of the players, do not necessarily
have a value if Nature has 3 or more choices. The value does exist if Nature has 2 choices. The value also does not necessarily
exist if Nature chooses from 2 Borel payoff functions. Similarly, if Player 1 chooses the Borel winning set and does not reveal
his selection to Player 2, then the game does not necessarily have a value if there are 3 or more choices; it does have a
value if there are only 2 choices. If Player 1 chooses from 2 Borel payoff functions and does not reveal his choice, the game
need not have a value either. 相似文献
93.
Let μ and ν be probability measures on a group Γ and let G
μ
and G
ν
denote Green’s function with respect to μ and ν. The group Γ is said to admit instability of Green’s function if there are symmetric, finitely supported measures μ and ν and a sequence {x
n
} such that G
μ
(e, x
n
)/G
ν
(e,x
n
) →0, and Γ admits instability of recurrence if there is a set S that is recurrent with respect to ν but transient with respect to μ. We give a number of examples of groups that have the Liouville property but have both types of instabilities. Previously
known groups with these instabilities did not have the Liouville property. 相似文献
94.
Onaya H Itai Y Ahmadi T Yoshioka H Okumura T Akine Y Tsuji H Tsujii H 《Magnetic resonance imaging》2001,19(1):41-46
The objective of this study was to assess the value of MR imaging in the differentiation between a recurrent hepatocellular carcinoma (HCC) and a radiation-induced hepatic injury. Nine male patients with suspected recurrence after radiotherapy for HCC underwent T(2)-, T(1)-weighted imaging and Gd-DTPA enhanced dynamic studies. T(2) relaxation times, signal intensity ratios in T(1)-weighted images (WI) and the relative enhancement of the dynamic study were calculated. Recurrent tumors and the irradiated area showed similar image characteristics: hypointense in T(1)-WI and hyperintense in T(2)-WI. T(2) values and signal intensity ratios in the T(1)-WI were not significantly different. In the gadolinium-enhanced dynamic study, a recurrent HCC showed early enhancement, followed by a rapid washout. However, the irradiated liver parenchyma showed hyperintensity from an early phase, and contrast enhancement tended to be more prominent and prolonged at the end of the dynamic studies. The characteristic findings of the dynamic MR study enable us to distinguish between a recurrent HCC and a radiation-induced hepatic injury. 相似文献
95.
Itai Einav 《International Journal of Solids and Structures》2012,49(11-12):1305-1315
A unifying theory of plasticity is developed that allows deducing models with either hypo-plastic, elasto-plastic or hyper-plastic constitutive structures. Elasto-plasticity is shown to be a singular case of hypo-plasticity. It is further demonstrated that certain conditions can be imposed to generate a new hierarchy of thermodynamically consistent hypo-plastic models, with a hyper-plastic structure as a singular case. The unifying theory is powerfully bridging between the tools created specifically for advancing models under either of those previous formulations. 相似文献
96.
We study the O(n) model on graphs quasi-isometric to the hyperbolic plane, with free boundary conditions. We observe that the pair correlation decays exponentially with distance, for all temperatures, if and only if \(n>1.\) 相似文献
97.
At high area fractions, monolayers of colloidal dimer particles form a degenerate crystal (DC) structure in which the particle lobes occupy triangular lattice sites while the particles are oriented randomly along any of the three lattice directions. We report that dislocation glide in DCs is blocked by certain particle orientations. The mean number of lattice constants between such obstacles is Z[over](exp)=4.6+/-0.2 in experimentally observed DC grains and Z[over](sim)=6.18+/-0.01 in simulated monocrystalline DCs. Dislocation propagation beyond these obstacles is observed to proceed through dislocation reactions. We estimate that the energetic cost of dislocation pair separation via such reactions in an otherwise defect free DC grows linearly with final separation, hinting that the material properties of DCs may be dramatically different from those of 2-D crystals of spheres. 相似文献
98.
The purpose of this study was to clarify the mechanism of transformation from alpha-form to beta-form via beta'-form of glyceryl monostearate (GM) and to determine the optimum conditions of heat-treatment for physically stabilizing GM in a pharmaceutical formulation. Thermal analysis repeated twice using a differential scanning calorimeter (DSC) were performed on mixtures of two crystal forms. In the first run (enthalpy of melting: DeltaH1), two endothermic peaks of alpha-form and beta-form were observed. However, in the second run (enthalpy of melting: DeltaH2), only the endothermic peak of the alpha-form was observed. From a strong correlation observed between the beta-form content in the mixture of alpha-form and beta-form and the enthalpy change, (DeltaH1-DeltaH2)/DeltaH2, beta-form content was expressed as a function of the enthalpy change. Using this relation, the stable beta-form content during the heat-treatment could be determined, and the maximum beta-form content was obtained when the heat-treatment was carried out at 50 degrees C. An inflection point existed in the time course of transformation of alpha-form to beta-form. It was assumed that almost all of alpha-form transformed to beta'-form at this point, and that subsequently only transformation from beta'-form to beta-form occurred. Based on this aspect, the transformation rate equations were derived as consecutive reaction. Experimental data coincided well with the theoretical curve. In conclusion, GM was transformed in the consecutive reaction, and 50 degrees C was the optimum heat-treatment temperature for transforming GM from the alpha-form to the stable beta-form. 相似文献
99.
Fresco ZM Suez I Backer SA Fréchet JM 《Journal of the American Chemical Society》2004,126(27):8374-8375
An alpha,alpha-dimethyl-3,5-dimethoxybenzyloxycarbonyl (DDZ)-protected amine monolayer can be selectively deprotected by the application of a voltage bias from a conducting AFM tip to afford localized nanoscale patterns that can be visualized by self-assembly of dendritic molecular objects with terminal carboxylic acid groups and different aspect ratios. 相似文献
100.
Ethene epoxidation with hydrogen peroxide was studied on hydroxylated binuclear metal sites, using DFT calculations at the B3LYP/6-311+G(d,p) level of theory. A decrease of the activation enthalpy of approximately 100 kJ mol(-1) was observed compared to the gas phase reaction between hydrogen peroxide and ethene. It was previously shown that micro-solvation with water reduces the activation enthalpy by approximately 77 kJ mol(-1) and only the additional 24 kJ mol(-1) can be attributed to the binuclear site. Three different metal centres were tested, Ti(iv), Si(iv) and Ge(iv), in order to investigate any specific role of the metal centre on the activation enthalpy. The results clearly show that the activation enthalpy is independent on the nature of the metal centre. This emphasises the role of the hydrogen bonded network provided by the hydroxylated metal sites, on the stabilisation of the transitions state. In ref. 1 (A. Lundin, I. Panas and E. Ahlberg, J. Phys. Chem. A, 2007, 111, 9080) it was demonstrated that, at the transition state and upon micro-solvation, the hydrogen peroxide entity becomes polarized within the hydrogen bonding network, forming a negatively-charged fragment distant from the ethene molecule and a positively-charged fragment directly involved in the oxygen insertion step. The same mechanism was found to hold also for the reaction at the binuclear catalytic site, since the required hydrogen bonding is effectively provided by the hydroxylated metal centres. This mechanism is compared to the two-step pathway which employs a metal peroxide intermediate. Both reaction channels were found to be plausible in confined environments. 相似文献