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101.
The ionization and appearance potentials for the molecular and [M ? Me]+ ions of several stereoisomeric methyl-1,3-oxathianes were measured. The differences between the ionisation and/or appearance potentials are shown to correlate well with the conformational energy differences in question.  相似文献   
102.
Hydrolysis and speciation of aluminium sulfate octadecahydrate Al2(SO4)3·18H2OAl2(SO4)3·18H2O was studied by electrospray time of flight mass spectrometry (ESI TOF MS). Several novel polymeric species were determined. Highly charged polymers, characterized by other methods, such as the Keggin cation [Al13O4(OH)24(H2O)12]7+ and the octameric aluminium hydroxide cluster [Al8(OH)14(H2O)18](SO4)5 16H2O, were found using ESI-MS as the anions [Al13O4(OH)25(SO4)4]2− and [Al8O(OH)14(SO4)5(H2O)4]2−. All the main species identified contained sulfate or hydrogen sulfate. The compositions of the determined ions mimicked those of several stable mineral forms.  相似文献   
103.
The kinetics of the radical reactions of CH3 with HCl or DCl and CD3 with HCl or DCl have been investigated in a temperature controlled tubular reactor coupled to a photoionization mass spectrometer. The CH3 (or CD3) radical, R, was produced homogeneously in the reactor by a pulsed 193 nm exciplex laser photolysis of CH3COCH3 (or CD3COCD3). The decay of CH3/CD3 was monitored as a function of HCl/DCl concentration under pseudo-first-order conditions to determine the rate constants as a function of temperature, typically from 188 to 500 K. The rate constants of the CH3 and CD3 reactions with HCl had strong non-Arrhenius behavior at low temperatures. The rate constants were fitted to a modified Arrhenius expression k = QA exp (−Ea/RT) (error limits stated are 1σ + Students t values, units in cm3 molecule−1 s−1): k(CH3 + HCl) = [1.004 + 85.64 exp (−0.02438 × T/K)] × (3.3 ± 1.3) × 10−13 exp [−(4.8 ± 0.6) kJ mol−1/RT] and k(CD3 + HCl) = [1.002 + 73.31 exp (−0.02505 × T/K)] × (2.7 ± 1.2) × 10−13 exp [−(3.5 ± 0.5) kJ mol−1/RT]. The radical reactions with DCl were studied separately over a wide ranges of temperatures and in these temperature ranges the rate constants determined were fitted to a conventional Arrhenius expression k = A exp (−Ea/RT) (error limits stated are 1σ + Students t values, units in cm3 molecule−1 s−1): k(CH3 + DCl) = (2.4 ± 1.6) × 10−13 exp [−(7.8 ± 1.4) kJ mol−1/RT] and k(CD3 + DCl) = (1.2 ± 0.4) × 10−13 exp [−(5.2 ± 0.2) kJ mol−1/RT] cm3 molecule−1 s−1.  相似文献   
104.
Chromium trioxide forms an adduct with zwitterionic quinolinic acid. The structure of the product was found to be (quinolinium-3-carboxylato-O)trioxidochromium(VI), determined by single-crystal X-ray diffraction methods. To evaluate the bonding properties of the compound, its structure was optimized at the B3LYP/6-311G* level of theory. The electronic characteristics were investigated by topological methods applied to the total charge density in various model compounds including the title compound, title compound with a HF molecule presenting a hydrogen bonding and anionic moiety. Calculated aromaticity indices indicate that the quinolinic rings tend to conserve their degree of aromaticity against hydrogen bonding. However, when there is hydrogen bonding involving an N-H bond or when the quinolinium zwitterion is deprotonated, there are clear changes in the interaction between chromium trioxide and the quinolinic moiety.   相似文献   
105.
The existence of the different R2+/R3+/RIV (R: rare earth) ions as well as the modifications in the structural environment around the dopant and co-dopants in CaAl2O4:Eu2+,R3+ persistent luminescence materials was studied by LIII edge X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) measurements at Hamburger Synchrotronstrahlungslabor (HASYLAB) at Deutsches Elektronen-Synchrotron (DESY) (Hamburg, Germany). The measurements were carried out at 10 and 296 K for selected rare earth (co-)dopants (Eu2+; Ce3+, Nd3+, Sm3+, and Yb3+).  相似文献   
106.
The electronic structures of the distrontium magnesium disilicate (Sr2MgSi2O7(:Eu2+)) materials were studied by a combined experimental and theoretical approach. The UV-VUV synchrotron radiation was applied in the experimental study while the electronic structures were investigated theoretically by using the density functional theory. The structure of the valence and conduction bands and the band gap energy of the material as well as the position of the Eu2+ 4f ground state were calculated. The calculated band gap energy (6.7 eV) agrees well with the experimental value of 7.1 eV. The valence band consists mainly of the oxygen states and the bottom of the conduction band of the Sr states. The calculated occupied 4f ground state of Eu2+ lies in the energy gap of the host though the position depends strongly on the Coulomb repulsion strength. The position of the 4f ground state with respect to the valence and conduction bands is discussed using the theoretical and experimental evidence available.  相似文献   
107.
The hydrolysis reactions of FeCl3 in 0.1 mM aqueous solutions were monitored by electrospray ionisation time-of-flight mass spectrometry (ESI-ToF-MS). In contrast to the other ionisation techniques, electrospray ionisation provides information on the composition of the elemental cores even in water and salt cluster ions. Therefore, the technique facilitates detection of the bonding of the chloride ions in the oxo-hydroxo-iron cores. A variety of mononuclear and polynuclear iron-oxohydroxo-chloride complexes were characterised from the cationic and anionic mass spectra of iron(III) solutions. Oxidation and reduction reactions of iron, as well as competition between OH- and Cl- ions within one iron core, were also observed.  相似文献   
108.
[structure: see text] The relative and absolute stereochemistry of the structurally unique 24-membered myxobacterial macrolides archazolid A and B, highly potent vacuolar-type ATPase (V-ATPase) inhibitors in vitro and in vivo, was determined on the basis of a combination of extensive high-field NMR studies, including J-based configuration analysis, molecular modeling, and chemical methods.  相似文献   
109.
Z-configured 1,4-diene or β, γ-unsaturated carbonyl systems are readily available by the Wittig reaction. Isomerization required for access into the E-series can easily be accomplished by irradiation using an ordinary tungsten lamp and diphenyl disulphide sensitizer. There is very little formatation of conjugated isomers (less than 1%).  相似文献   
110.
The details of the mechanism of persistent luminescence were probed by investigating the trap level structure of Sr2MgSi2O7:Eu2+,R3+ materials (R: Y, La-Lu, excluding Pm and Eu) with thermoluminescence (TL) measurements and Density Functional Theory (DFT) calculations. The TL results indicated that the shallowest traps for each Sr2MgSi2O7:Eu2+,R3+ material above room temperature were always ca. 0.7 eV corresponding to a strong TL maximum at ca. 90 °C. This main trap energy was only slightly modified by the different co-dopants, which, in contrast, had a significant effect on the depths of the deeper traps. The combined results of the trap level energies obtained from the experimental data and DFT calculations suggest that the main trap responsible for the persistent luminescence of the Sr2MgSi2O7:Eu2+,R3+ materials is created by charge compensation lattice defects, identified tentatively as oxygen vacancies, induced by the R3+ co-dopants.  相似文献   
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