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971.
C. I. Ratcliffe S. K. Garg D. W. Davidson 《Journal of inclusion phenomena and macrocyclic chemistry》1990,8(1-2):159-175
Polycrystalline (CH3)4NOH·5 H2O (I) and (CH3)4NOD·5D2O (II) have been studied by1H NMR lineshapes, second moments and spin-lattice relaxation times and by2H NMR lineshapes as a function of temperature. From low temperatures the first motion to occur is reorientation of the internally rigid (CH3)4N+ ion about a uniqueC
3
axis (E
ta
= 8.37 kJ/mol forI,E
a
= 9.00 kJ/mole forII), followed closely by pseudo isotropic reorientation of the whole ion (E
a
= 18.10 kJ/mol). Motion of the cage molecules (water and hydroxide ion) occurs at higher temperatures with an apparentE
a
= 11.30 kJ/mol. There is some evidence of a phase transition inII but notI in the 220–230 K region.2H NMR lineshapes ofII below 220 K indicate static cage molecules. Some of the2H quadrupole coupling constants derived from these spectra correspond to O·O hydrogen-bond distances which are incompatible with the known room temperature structure ofI. Above the possible transition inII the anisotropic2H lineshapes indicate rapid motion of2H among all possible hydrogen-bond sites via transfer along the bonds and molecular reorientation. This motion persists in the high temperature phase but the lineshape becomes isotropic due to the cubic symmetry of this phase. It is possible that1H or2H tunnelling plays an important part in the motion of the cage molecules and the different phase behaviour ofI andII.Dedicated to Dr D. W. Davidson in honor of his great contributions to the sciences of inclusion phenomena. 相似文献
972.
Co_xFe_(3-x)O_4晶体属尖晶石型结构,具有良好的磁光效应及化学稳定性。在尖晶石型铁氧体中,金属离子存在着A-A、B-B和A-B晶位间超交换作用,其中以A-B间的超交换作用最强。超交换作用引起不同次晶格的磁矩反向排列,而铁氧体的亚铁磁性则来源于晶格中A、B位上未抵消的反向磁矩。尖晶石型单一铁氧体MFe_2O_4晶格中离子分布通常为Fe_xM_(1-x)[M_xFe_(2-x)]O_4。在三价铁盐和二价钴盐混合水溶液中滴加碱液可制备CoFe_2O纳米晶。本文用改进的化学共沉淀法,以不同摩尔浓度的Co(Ⅱ)和Fe(Ⅱ)合成Co_xFe_(3-x)O_4纳米晶系列样品,考察了样品组成与其磁性的关系。 相似文献
973.
1H and 13C NMR spectra and 1H spin-lattice relaxation times T1 and T1ρ have been employed to study the structure and molecular dynamics in polyethylene and ethylene-1-butene copolymer in the temperature range from 100 to 370 K. Results are interpreted in terms of α, β and γ -relaxation, as well as methyl group rotation. The activation energies for all motions were established. The incorporation of 1-butene into ethylene chain leads to an increase of mobility in amorphous and crystalline phases as well as appearance the 13C resonance characteristic to the monoclinic structure in addition to the orthorhombic observed in both polymers. The crystallinity degree derived from T1ρ in studied polymers is close to that determined using DSC method. 相似文献
974.
We present an approach for calculating local electric dipole moments for fragments of molecular or supramolecular systems. This is important for understanding chemical gating and solvent effects in nanoelectronics, atomic force microscopy, and intensities in infrared spectroscopy. Owing to the nonzero partial charge of most fragments, “naively” defined local dipole moments are origin‐dependent. Inspired by previous work based on Bader's atoms‐in‐molecules (AIM) partitioning, we derive a definition of fragment dipole moments which achieves origin‐independence by relying on internal reference points. Instead of bond critical points (BCPs) as in existing approaches, we use as few reference points as possible, which are located between the fragment and the remainder(s) of the system and may be chosen based on chemical intuition. This allows our approach to be used with AIM implementations that circumvent the calculation of critical points for reasons of computational efficiency, for cases where no BCPs are found due to large interfragment distances, and with local partitioning schemes other than AIM which do not provide BCPs. It is applicable to both covalently and noncovalently bound systems. © 2016 Wiley Periodicals, Inc. 相似文献
975.
Recently, the diverse properties of Rydberg atoms, which probably arise from its large electric dipole moment(EDM),have been explored. In this paper, we report electric dipole moments along with Stark energies and charge densities of lithium Rydberg states in the presence of electric fields, calculated by matrix diagonalization. Huge electric dipole moments are discovered. In order to check the validity of the EDMs, we also use these electric dipole moments to calculate the Stark energies by numerical integration. The results agree with those calculated by matrix diagonalization. 相似文献
976.
A quantum effect characterized by a dependence of the angular frequency associated with the confinement of a neutral particle to a quantum ring on the quantum numbers of the system and the Aharonov–Casher geometric phase is discussed. Then, it is shown that persistent spin currents can arise in a two-dimensional quantum ring in the presence of a Coulomb-type potential. A particular contribution to the persistent spin currents arises from the dependence of the angular frequency on the geometric quantum phase. 相似文献
977.
Akane Agui Hiroshi Sakurai Takuro Tamura Toshitaka Kurachi Masahito Tanaka Hiromichi Adachi Hiroshi Kawata 《Journal of synchrotron radiation》2010,17(3):321-324
An application of magnetic Compton scattering as a new tool to measure a spin‐specific magnetic hysteresis (SSMH) loop is introduced and its validity demonstrated. The applied magnetic field dependence of the integrated intensity of magnetic Compton scattering spectra, which reflect only the spin‐dependent magnetic properties of magnetically active electrons, was interpreted as the spin‐specific hysteresis. The spin magnetization of amorphous Tb33Co67 film was observed and its SSMH loop exhibited qualitative agreement with the ordinal magnetic hysteresis loop measured using a conventional vibrating sample magnetometer. 相似文献
978.
给出一类较广泛的$\widetilde{\rho}$ 混合序列的矩不等式. 讨论了$\widetilde{\rho}$ 混合序列的完全收敛性, 所得的结果改进了相关文献中的结果,并得到了完全收敛速度与矩条件之间的等价关系. 相似文献
979.
RING Peter 《中国科学:物理学 力学 天文学(英文版)》2011,(2)
The g factors and spectroscopic quadrupole moments of low-lying excited states 2+1,…,81+ in 24Mg are studied in a covariant density functional theory.The wave functions are constructed by configuration mixing of axially deformed mean-field states projected on good angular momentum.The mean-field states are obtained from the constraint relativistic point-coupling model plus BCS calculations using the PC-F1 parametrization for the particle-hole channel and a density-independent delta-force for the particle-pa... 相似文献
980.
By the substitution of one methyl group in Neopentane C(CH3)4 with a methylchlorid group the globular sphere is expanded in 1‐chloro‐2,2‐dimethylpropane (CH3)3C(CH2Cl). With the aid of DSC measurements, X‐ray powder diffraction, 1H NMR and 35Cl NQR measurements two orientationally disordered (plastic) phases were established. The low temperature structure was solved and a structural model of phase II is proposed. A mechanism to describe the reorientation in the different phases is given as well as a connectivity scheme between the phases is discussed. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献