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91.
92.
We present experimental results describing the influence of optical bias on the transient characteristics of gratings formed in photorefractive BSO. A transient peak is evident, and the properties of this peak can be controlled by suitable adjustment of the relative intensities of the optical beams involved. 相似文献
93.
94.
Daniel T. Gillespie 《Foundations of Physics》1995,25(7):1041-1053
Quantum mechanics posits that the wave function of a one-particle system evolves with time according to the Schrödinger equation, and furthermore has a square modulus that serves as a probability density function for the position of the particle. It is natural to wonder if this stochastic characterization of the particle's position can be framed as a univariate continuous Markov process, sometimes also called a classical diffusion process, whose temporal evolution is governed by the classically transparent equations of Langevin and Fokker-Planck. It is shown here that this cannot generally be done in a consistent way, despite recent suggestions to the contrary. 相似文献
95.
Todd A. Gillespie Richard A. Yost 《Journal of the American Society for Mass Spectrometry》1990,1(5):389-396
Some intriguing discoveries were made concerning the collision-activated dissociation behavior of the derivatized carboxylate anions of PGE2 and PGF2α. The carboxylate anion [MPFB]? formed from electron-capture negative chemical ionization of the pentafluorobenzyl ester-trimethylsilyl derivative of PGF2α showed little fragmentation under typical collision gas pressures and energies (<2.0 mtorr N2 and <20 eV). In contrast, the daughter spectra of the carboxylate anion of the methoxime-pentafluorobenzyl ester-trimethylsilyl derivative of PGE2 produced many intense fragments under the same conditions. 相似文献
96.
97.
98.
J. L. Oscarson S. E. Gillespie R. M. Izatt X. Chen C. Pando 《Journal of solution chemistry》1992,21(8):789-801
The aqueous reaction, HNO3(aq)=H++NO
3
–
was studied as a function of ionic strength I at 250, 275, 300 and 319°C using a flow calorimeter and the equilibrium constant K and enthalpy change (H) at I=0 were determined. Using these experimental values, equations describing logK, H, the entropy change S and the heat capacity change C
p
of reaction at I=0 and temperatures from 250 to 319°C were derived. The increasing importance of ion association as temperature rises was discussed. The use of an equation containing identical numbers of positive and identical numbers of negative charges on both sides of the equal sign (isocoulombic reaction principle) was applied to the logK values reported here and to those determined by others. The resulting plot of logK for the isocoulombic reaction vs. 1/T was fairly linear which supports the postulate that the principle is a useful technique for the extrapolation of logK values from low to high temperatures.Presented at the Second International Symposium on Chemistry in High Temperature Water, Provo, UT, August 1991. 相似文献
99.
The recent experimental determination of the geometry of Ti(CH3)2Cl2 shows it to be inconsistent with the VSEPR model, a result not uncommon for molecules containing transition metal atoms. The valence shell charge concentrations (CCs) that appear as maxima in L(r)=−2ρ(r), provide a physical basis for the VSEPR model of molecular geometry for main group molecules. The same model accounts for the geometry of transition metal molecules with the proviso that the CCs are formed within the outer shell of the core of the metal atom, as defined by the shell structure of L(r). This observation appears to be in conflict with calculations for Ti(CH3)2Cl2 showing that its geometry can be predicted using an effective core potential for the metal atom, a procedure that would appear to preclude the presence of core distortions. The apparent contradiction is resolved by distinguishing between the definition of the core using L(r) and one based on the orbital model. 相似文献
100.
We have studied the geometry of the formally d(0) MX(n)() (X = F, H, CH(3) and O; n = 2-6) molecules of the period 4 metals from Ca to Mn by studying the topology of the electron localization function (ELF) in order to try to understand why many of these molecules have non-VSEPR geometries. The quantitative analysis of the core basin population shows that it is always larger than its conventional value (18) because, in the LCAO-MO scheme, the 3d basis functions centered on the metal noticeably contribute to the electron density within the core region associated with the M shell. Therefore, the density available to form the bonds is less than Z(M) - 18, the value adopted in electron counts. Under the influence of the ligands, these electrons cause the core to lose its spherical symmetry by the formation of opposite-spin pair localization basins, which in turn influence the geometry of the ligands if the interaction of the ligands with the core is sufficiently strong. All of the ligands considered in this study, except F, interact with the core sufficiently strongly to give non-VSEPR geometries, which we have rationalized on the basis of the ELF topology. 相似文献