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1.
Catalytic activity of Os(VIII) in the oxidation of some twenty organic sulfides with sodium salt of N-chlorobenzenesulfonamide (CAB) has been investigated in alkaline (pH8.7) t-butanol–water (1:1 v/v) medium. Significant retarding influence of [OH] on the reactivity is exhibited. The catalysed reaction is strongly accelerated in the presence of Hg(II). Imperfections are observed in the linear Hammett relationship in the case of –NO2 substituents.  相似文献   
2.
Summary The influence of calcite, dolomite, pyrite and vaterite on the kinetics of uranium release from a natural rock under relevant, i.e., field conditions has been investigated. The time dependence of the U release has been studied in two different experimental procedures (open and closed systems) at laboratory temperature (21±2 °C). Performing batch experiments in tap water, the U release efficiency of a natural U-bearing rock was characterized in the presence of varying amounts of three different carbonate bearing minerals for experimental durations of up to 782 days. Another experiment was conducted for a period of 14 days in the presence of a pyrite mineral. The results demonstrate that the presence of carbonate minerals does not have any significant influence on U release in closed systems where the U concentration at saturation was ca. 54 mg/l. In contrast, in open systems, the U concentration was ca. 8 mg/l at saturation and the effects of all additives both on kinetics and saturation concentration of U were apparent.  相似文献   
3.
A comprehensive photophysical study of the linear and nonlinear absorption properties has been carried out on two series of two-photon absorbing dyes to gain insight into how structure-property relationships influence observed nonlinear absorption. The materials studied consist of an electron accepting benzothiazole group connected to an electron donating diphenylamine via a fluorene bridging group. Two series differ from each other by the addition of one phenyl group and for each series one-arm (dipolar, AF240 and AF270), two-arm (quadrupolar, AF287 and AF295), and three-arm (octupolar, AF350 and AF380) versions were studied. Overall the AF240 series exhibits higher intrinsic two-photon absorption (TPA) cross-sections than the AF270 series as well as enhanced nanosecond nonlinear absorption, with an increase with number of branches. The enhanced nanosecond nonlinearity is understood by taking into account the contribution from the singlet and triplet excited states and was verified by a two-photon assisted excited-state absorption model that satisfactorily predicts the nonlinear absorption of the chromophores.  相似文献   
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An analytic treatment of localization in a weakly disordered system is presented for the case where the real lattice is approximated by a Cayley tree. Contrary to a recent assertion we find that the mobility edge moves inwards into the band as disorder increases from zero.  相似文献   
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A suite of keV polyatomic or 'cluster' projectiles was used to bombard unoxidized and oxidized self-assembled monolayer surfaces. Negative secondary ion yields, collected at the limit of single ion impacts, were measured and compared for both molecular and fragment ions. In contrast to targets that are orders of magnitude thicker than the penetration range of the primary ions, secondary ion yields from polyatomic projectile impacts on self-assembled monolayers show little to no enhancement when compared with monatomic projectiles at the same velocity. This unusual trend is most likely due to the structural arrangement and bonding characteristics of the monolayer molecules with the Au(111). Copyright 1999 John Wiley & Sons, Ltd.  相似文献   
8.
Current methods for stable oxygen isotopic (delta (18)O) analysis of soil water rely on separation of water from the soil matrix before analysis. These separation procedures are not only time consuming and require relatively large samples of soil, but also have been shown to introduce a large potential source of error. Current research at Queen's University Belfast is focused on using direct equilibration of CO(2) with the pore water to eliminate this extraction step using the automated Multiprep system and a Micromass Prism III isotope ratio mass spectrometer (IRMS). The findings of this research indicate the method is less time consuming, more reliable, and reproducible to within accepted limits (+/-0.1% per thousand delta (18)O). In this study the direct equilibration method is used to analyse delta (18)O tracer profiles in the unsaturated zone of field soils, concurrently with chloride tracer profiles, which can be used to assess infiltration rates and mechanisms through the unsaturated zone. Copyright 1999 John Wiley & Sons, Ltd.  相似文献   
9.
The time-dependent hamiltonian formulation of the Langevin equation is used as a starting point for a quantum treatment of the motion of a free Brownian particle. From an exact solution of the time-dependent Schrödinger equation for the density-matrix in one dimension we obtain the mean square displacement, x 2(t), of the Brownian particle, as well as the mean displacement induced by a uniform electric fieldE(t). While quantum effects are significant for time intervals up to the frictional relaxation time, the long time results are identical to those obtained directly from the solution of the Langevin equation. Next, we analyse in a similar way the motion of an electron in a dynamically disordered continuum where the effect of a classical friction force (dissipation) is taken into account. The friction effect is described using the phenomenological time-dependent hamiltonian inferred from the Langevin equation and the potential fluctuations are assumed to have a generalized gaussian white-noise form. The final result for x 2 (t) shows a time-dependence similar to that obtained for the case of Brownian motion. In particular, it corresponds to diffusive behavior at long times, in contrast to thet 3-dependence obtained in a recent study for the case where friction is absent.  相似文献   
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