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61.
We investigate polyelectrolyte bridging interactions mediated by charged, flexible, polyelectrolyte chains between fixed cylindrical macroions of opposite charge in a two-dimensional hexagonal crystalline array. We show that in the asymptotic regime of small macroion density, the polyelectrolyte-mediated attraction is long range, falling off approximately linearly with the macroion array density. We investigate the polyelectrolyte free energy as a function of the macroion density and derive several analytic limiting laws valid in different regimes of the parameter space. 相似文献
62.
63.
An amorphous ultra-thin film of Fe2O3 was prepared on partially oriented graphite (Papyex) by surface oxidation of an adsorbed monolayer of Fe(CO)5. Mössbauer spectra exhibit super-paramagnetism below 79 K. The Mössbauer fraction parallel to the film exceeds that perpendicular by 16% at room temperature. 相似文献
64.
We consider the linearized time-dependent Navier-Stokes equation including finite compressibility and viscosity. We first
constitute the Green's function, from which we derive the flow profiles and response functions for a plane, a sphere and a
cylinder for arbitrary surface slip length. For high driving frequency the flow pattern is dominated by the diffusion of vorticity
and compression, for low frequency compression propagates in the form of sound waves which are exponentially damped at a screening
length larger than the sound wave length. The crossover between the diffusive and propagative compression regimes occurs at
the fluid's intrinsic frequency w \omega ∼ c
2
r0 \rho_{0}^{}/h \eta , with c the speed of sound, r0 \rho_{0}^{} the fluid density and h \eta the viscosity. In the propagative regime the hydrodynamic response function of spheres and cylinders exhibits a high-frequency
resonance when the particle size is of the order of the sound wave length. A distinct low-frequency resonance occurs at the
boundary between the propagative and diffusive regimes. Those resonant features should be detectable experimentally by tracking
the diffusion of particles, as well as by measuring the fluctuation spectrum or the response spectrum of trapped particles.
Since the response function depends sensitively on the slip length, in principle the slip length can be deduced from an experimentally
measured response function. 相似文献
65.
The segregation of solute particles on a moving interface leads to the appearance of two types of instabilities near competing velocity thresholds. This behavior is shown to occur in a variety of exactly solvable models where the interface motion is coupled to a diffusion process of the solute particles. These models directly apply to the propagation of internal domain walls, but can also be generalized to surfaces of growing crystals in the kinetics-limited regime. 相似文献
66.
Puchta R van Eikema Hommes N Meier R van Eldik R 《Dalton transactions (Cambridge, England : 2003)》2006,(28):3392-3395
Based on DFT calculations (RB3LYP/LANL2DZp), the unexpected single-line 1H NMR spectrum of Zn(II)(nta), nta = 2,2',2'-nitrilotriacetate, can be ascribed to a non-dissociative enantiomerization process (deltadeltadelta<=>lambdalambdalambda) from C3viaC3v to C3 symmetry. The energy barrier is rather low and depends to a lesser extent on the nature of the co-ligand in [Zn(nta)X]2- (X: H-, CH3- NH2-, OCH3-, F-, Cl-, Br-, I-) and [Zn(nta)Y]- (Y: NCH, CO, N2, O(CH3)2), but more so on the overall charge of the complex. The energy barrier for enantiomerization of [Zn(nta)X]2- is between 5.7 and 6.7 kcal mol-1, and for [Zn(nta)Y]- between 2.2 and 3.1 kcal mol-1. 相似文献
67.
Bugarcić ZD Nandibewoor ST Hamza MS Heinemann F van Eldik R 《Dalton transactions (Cambridge, England : 2003)》2006,(24):2984-2990
Substitution reactions of the complexes [Pd(bpma)(H2O)]2+, [Pd(bpma)Cl]+, [Pd(dien)(H2O)]2+ and [Pd(dien)Cl]+, where bpma = bis(2-pyridylmethyl)amine and dien = diethylentriamine or 1,5-diamino-3-azapentane, with some nitrogen-donor ligands such as triazole, pyrazole, pyrimidine, pyrazine and pyridazine, were studied in an aqueous 0.10 M NaClO4 at pH 2.8 using variable-temperature and -pressure stopped-flow spectrophotometry. The second-order rate constants indicate that the Pd(II) complexes of bpma, viz. [Pd(bpma)(H2O)]2+ and [Pd(bpma)Cl]+, are more reactive than the complexes of dien, viz. [Pd(dien)(H2O)]2+ and [Pd(dien)Cl]+. Also, the aqua complexes, [Pd(bpma)(H2O)]2+ and [Pd(dien)(H2O)]2+, are much more reactive than the corresponding chloro complexes. The most reactive nucleophile of the five-membered rings is triazole and for the six-membered rings the most reactive one is pyridazine. Activation parameters were determined for all reactions and the negative entropies and volumes of activation (Delta S++, Delta V++) support an associative ligand substitution mechanism. The crystal structure of [Pd(bpma)(H2O)](ClO4)2.2H2O was determined by X-ray diffraction. Crystals are monoclinic with the space group P2(1)/c. The coordination geometry of [Pd(bpma)(H2O)]2+ is distorted square-planar. The Pd-N (central) bond distance, 1.958(5) A, is shorter than the other two Pd-N distances, 2.007(5) and 2.009(5) A. The Pd-O distance is 2.043(5) A. 相似文献
68.
Rudi Penne 《Discrete Mathematics》2010,310(4):966-969
We consider words over a finite alphabet with certain uniqueness properties (a subsequence of length k does not occur more than once) and distance properties (at least j other symbols separate the occurrence of the same symbol). The maximal length of these words is realised by linear de Bruijn sequences with certain forbidden subsequences. We prove the existence of these maximal sequences. 相似文献
69.
Coropceanu E. Rudic V. Cepoi L. Rudi L. Lozan V. Chiriac T. Miscu V. Bulhac I. Kravtsov V. Bourosh P. 《Russian Journal of Coordination Chemistry》2019,45(3):200-207
Russian Journal of Coordination Chemistry - New fluorine-containing cobalt(III) dioximates [Co(DmgH)2(Thio)2]2F[PF6] (I) and [Co(DmgH)2(Sam)2]2[TiF6] · 4H2O (II) (DmgH = dimethylglyoxime... 相似文献
70.
Hiromasa Nishikiori Rudi Agus Setiawan Kyohei Miyashita Katsuya Teshima Tsuneo Fujii 《Photochemistry and photobiology》2014,90(4):747-759
Fluorescein‐dispersing titania gel films were prepared by the acid‐catalyzed sol–gel reaction using a titanium alkoxide solution containing fluorescein. The molecular forms of fluorescein in the films, depending on its acid–base equilibria, and the complex formation and photoinduced electron transfer process between the dye and titania surface were investigated by fluorescence and photoelectric measurements. The titanium species were coordinated to the carboxylate and phenolate‐like groups of the fluorescein species. The quantum efficiencies of the fluorescence quenching and photoelectric conversion were higher upon excitation of the dianion species interacting with the titania, i.e. the dye–titania complex. This result indicated that the dianion form was the most favorable for formation of the dye–titania complex exhibiting the highest electron transfer efficiency. Using nitric acid as the catalyst, the titania surface bonded to the fluorescein instead of the adsorbed nitrate ion during the steam treatment. The dye–titania complex formation played an important role in the electron injection from the dye to the titania conduction band. 相似文献