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1.
T. Rajagopalan J.A. Lubguban S. Gangopadhyay J. Sun S.L. Simon R. Butler 《Applied Surface Science》2006,252(18):6323-6331
Hexamethyldisilazane (HMDS) vapor treatment of plasma-damaged nanoporous organosilicate thin films has been studied as a function of treatment temperature in this work. Although, the HMDS vapor treatment facilitated incorporation of methyl (CH3) groups subsequent to the removal of free hydroxyl (OH) groups in the damaged films at treatment temperature as low as 55 °C, the bonded OH groups were not removed. More significantly, detailed analysis of the results reveals that HMDS vapor modified only the surface of the plasma-damaged samples and not the entire film as expected. This is attributed to the formation of a thin solid layer on the surface, which effectively prevents penetration of HMDS vapors into the bulk. The Fourier transform-infrared (FT-IR) absorption and dielectric constant measurements confirm that the vapor treatment assists only partial curing of the plasma-damaged films. Alternative processes of curing the films with HMDS dissolved in supercritical carbon dioxide (SCCO2) as a medium of reaction in static and pulsed modes were also attempted and the results are presented in this paper. 相似文献
2.
We consider the cooling of vibrational degrees of freedom in a photoinduced excited electronic state of a model molecular system. For the various parameters of the potential surfaces of the ground and excited electronic states and depending on the excitation frequency of a single-mode laser light, the average energy or average vibrational temperature of the excited state passes through a minimum. The amount of cooling is quantified in terms of the overlap integral between the ground and excited electronic states of the molecule. We have given an approach to calculate the Franck-Condon factor for a multimode displaced-distorted-rotated oscillator surface of the molecular system. This is subsequently used to study the effect of displacement, distortion, and Duschinsky rotation on the vibrational cooling in the excited state. The absorption spectra and also the average energy or the effective temperature of the excited electronic state are studied for the above model molecular system. Considering the non-Condon effect for the symmetry-forbidden transitions, we have discussed the absorption spectra and average temperature in the excited-state vibrational manifold. 相似文献
3.
K. P. Madhusudanan Shubhra Mittal Susheel Durani R. S. Kapil 《Journal of mass spectrometry : JMS》1985,20(5):323-326
Stereospecific adduct ion formation has been observed in the chemical ionization mass spectra (positive and negative) of certain E- and Z-1,2,3-triaryl-2-propen-1-ones. The Z isomers are found to give higher relative abundances of adduct ions than the E isomers. This has been interpreted in terms of the differences in the proton affinities of the isomers originating from their different degrees of enone resonance. Halide ion (CI? and Br?) attachment spectra of these compounds also show stereochemical differences in the relative abundances of [M]?˙ and [M+halide]? ions, though the effect is not as pronounced as in the case of the positive ion spectra. 相似文献
4.
Summary The kinetics of reduction of [MnIII(cydta)]– (where H4cydta=trans-cyclohexane-1,2-diamine-N N N' N'-tetraacetic acid) by some thiourea reductants have been studied in aqueous solution by stopped-flow techniques in the pH ranges 2.5–4.5 and 9.2–10.2. An initial increase in absorbance followed by a steady decrease indicated the formation of a precursor complex prior to the electron transfer step. The reactions are first order in both oxidant and reductant. The observed increase in rate in going from low to high pH is attributed to the difference in reactivities of the aqua and hydroxo species of the MnIII complex; the higher reactivity of the latter is consistent with the formation of a ligand-bridged activated species prior to electron transfer. The reactivity order for the thiourea derivatives follows the order of their reported substituent effects. 相似文献
5.
The reduction of triphenyltin piperidyl dithiocarbamate in acetone has been investigated using d.c. polarography and cyclic
voltammetry. Polarographic reduction yielded four well-defined waves, two of which were diffusion-controlled and two of which
appear to represent adsorption processes. The cyclic voltammetric study yielded results in close agreement with the polarographic
data. Results appear to indicate the release of the dithiocarbamate moiety, followed by reduction to form the triphenyltin
radical, which undergoes dimerization, as well as reduction to the triphenyltin anion. For comparison, the polarographic reduction
of triphenyltinchloride was investigated. A mechanism similar to that proposed by earlier authors for the polarographic behaviour
of tributyltin oxide was found.
For convenience, the more commonly used terminology of piperidyl dithiocarbamate is used throughout the paper, in place of
(piperidine-1-carbodithioato) triphenyltin (IV). 相似文献
6.
7.
Summary In NH4NO3+NH4OH buffered 10% (v/v) dioxan-water media (pH 7.0–8.5), thePseudo-first-order rate constant for the formation of the title complexes M(baen),i.e. ML, conforms to the equation 1/kobs=1/k+1/(kKo.s · TL), where TL stands for the total ligand concentration in the solution, Ko.s is the equilibrium constant for the formation of an intermediate outer sphere complex and k is the rate constant for the formation of the complex ML from the intermediate. Under the experimental conditions the free ligand (pKa>14) exists virtually exclusively in the undissociated form (baenH2 or LH2) which is present mostly as a keto-amine in the internally hydrogen-bonded state. Although the observed formation-rate ratio kCu/kNi is of the order of 105, as expected for systems having normal behaviour, the individual rate constants are very low (at 25°C, kCu=50 s–1 and kNi=4.7×10–4s–1) due to the highly negative S values (–84.2±3.3 JK–1M–1 for CuL and –105.8±4.1 JK–1M–1 for NiL); the much slower rate of formation of the nickel(II) complex is due to higher H value (41.2±1.0 kJM–1 for CuL and 78.2±1.2 kJM–1 for NiL) and more negative S value compared to that of CuL. The Ko.s values are much higher than expected for simple outer-sphere association between [M(H2O)6] and LH2 and may be due to hydrogen bonding interaction.In acid media ([H+], 0.01–0.04 M) these complexes M(baen) dissociate very rapidly into the [M(H2O)6]2+ species and baenH2, followed by a much slower hydrolytic cleavage of the ligand into its components,viz. acetylacetone and ethylenediamine (protonated). For the dissociation of the complexes kobs=k1[H+]+k2[H+]2. The reactions have been studied in 10% (v/v) dioxan-water media and also ethanolwater media of varying ethanol content (10–25% v/v) and the results are in conformity with a solvent-assisted dissociativeinterchange mechanism involving the protonated complexes. 相似文献
8.
Ashis Kumar Pondit Asim Kumar Das Soma Gangopadhyay Debabrata Banerjea 《Transition Metal Chemistry》1988,13(6):437-439
Summary Acid catalysed dissociation of the copper(II) and nickel(II) complexes (ML2+ of the quadridentate macrocyclic ligand 1, 5, 9, 13-tetraaza-2, 4, 4, 10, 12, 12-hexamethyl-cyclohexadecane-1, 9-diene (L) has been studied spectrophotometrically. Both complexes dissociate quite slowly with the observed pseudo-first order rate constants (kobs) showing acid dependence; for the nickel(II) complex (kobs)=kO+kH[H+], the ko path is however absent with the copper(II) complex. At 60°C (I=0.1M) the kH values areca 10–4 M–1 s–1 for both complexes; k
H
Cu
/k
H
Ni
=ca. 3.9, comparable to some other square-planar complexes of these metal ions. The rate difference is primarily due to H values [copper(II) complex, 29.4±0.5 kJ mol–1; nickel(II) complex, 35.6±1.5 kJ mol–1] with highly negative S values [for copper(II), –215.5 ±6.1 JK–1 mol–1 and for nickel(II), –208.1 ±5.6 JK–1 mol–1] which are much higher than the entropy of solvation of Ni2+ (ca. –160 JK–1 mol–1) and Cu2+ (ca. –99 JK–1 mol–1) ions; significant solvation of the released metal ions and the ligand is indicated. 相似文献
9.
The kinetics of substitution of aqua ligands fromcis-diaqua-bis(biguanide)cobalt(III) and chromium(III) ions by aspartic acid in EtOH–H2O media have been studied spectrophotometrically in the 30 to 45°C range. We propose the following rate law for the anation
相似文献
10.
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