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1.
3d-metal antimonides: Fe1+x Sb, N+x Sb, Co+x Sb and the (Ni1?y Fe y )Sb solid solution have been studied by the Mössbauer effect method at 57Fe and 119Sn. It was found that the quadrupole interactions at the Fe and Sn nucleus in 3d-metal antimonides are very sensitive to the filling of different crystallographic sites with metal atoms. The metal atoms in trigonal-bipyramidal sites have a strong effect on the quadrupole splitting of 119Sn. They are nearest to anions (Sb or Sn) with the typical axial ratio of c/a = 1.25. The QS(x) dependence of 119 Sn in 3d-metal antimonides in the 0 ≤ x ≤ 0.1 concentration range can be used to determine x – the concentration of transition metal excess relative to the stoichiometric composition. 相似文献
2.
S. S. Yarovoi S. F. Solodovnikov Z. A. Solodovnikova Yu. V. Mironov V. E. Fedorov 《Journal of Structural Chemistry》2006,47(1):97-101
A cluster complex of the composition [Th(DMSO)8Cl][Re6Se7Cl7] has been obtained by interaction of ThCl4 solution in DMSO with a water solution of K3[Re6Se7Cl7] and KCl. The compound crystallizes in the rhombic space group Pbcm with unit cell parameters a = 12.262(2) Å, b = 19.653(6) Å, c = 23.603(6) Å, V = 5688(2) Å3, Z = 4, d calc = 3.282 g/cm3. The structure is built from centrosymmetric cluster anions [Re6Se7Cl7]3? and complex cations [Th(DMSO)8Cl]3+ possessing mirror-plane symmetry, half of the DMSO ligands being doubly disordered. 相似文献
3.
Yu. V. Mironov S. F. Solodovnikov V. E. Fedorov Yu. V. Gatilov 《Journal of Structural Chemistry》2004,45(5):874-878
The reaction of a water solution of K4Re6Te8(CN)6 with a solution of Mn(NO3)2 in 0.02M hydrochloric acid in the presence of DMF gave crystals of a cluster rhenium complex [{ Mn(H2O)2(DMF)}2Re6Te8(CN)6]·2H2O. The structure of the compound was determined by single crystal X-ray diffraction (a = 12.6679(9) Å, b = 17.4524(12) Å, c = 9.7882(6) Å, β = 105.570(6)°, V = 2084.6(3) Å3, Z = 2, space group P21/n, R = 0. 0389). In the complex, the [Re6Te8(CN)6]4− cluster anions are linked to Mn2+ cations by the cyanide bridges, the manganese cations being additionally coordinated by the DMF molecule and two water molecules. The neighboring clusters are joined by Re-C-N-Mn bridges into a three-dimensional framework possessing cavities filled with doubly disordered water molecules.Original Russian Text Copyright © 2004 by Yu. V. Mironov, S. F. Solodovnikov, V. E. Fedorov, and Yu. V. Gatilov__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 5, pp. 918–922, September–October, 2004. 相似文献
4.
The results of quantum chemical calculations of the electronic structure and geometry of octahedral clusters [Mo6S8(CN)6]6−, [Mo6Se8(CN)6]6−, [Re6S8(CN)6]4−, and Rh6(CO)16 by the ab initio SCF (RHF) and DFT (B3LYP) methods with various basis sets are presented. The electronic states of the clusters under study
in ideal spherically symmetric potential were classified in the orbital quantum number l (1s, 1p, 1d, 1f, 1g, 1h, 1i), l = 0–6. In real crystal field with Oh symmetry these states are split. The calculated new electronic states were matched to the irreducible representations of
the point symmetry group Oh. The polarizabilities of the compounds considered are 55–65 Å3. A new model for the electronic structure of octahedral clusters containing M6 groups was proposed. The model is based on the idea of free electrons moving in spherically symmetric potential field.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2617–2624, December, 2005. 相似文献
5.
Cis-dioxo-metal complex ( NH3CH2CH2NH2 ) 2.5 [ Mo0.5^(V)W0.5^(VI)O2 ( OC6H4O ) 2] 1 was obtained by the reaction of tetra-butyl ammonium hexamolybdotungstate with 1, 2-dihydroxybenzene in the mixed solvent of CH3OH, CH3CN and ethylenediamine,and characterized by X-ray diffraction, UV-vis and EPR analysis. Compared with its analogous complexes (NH3CH2CH2NH2)3[Mo^(V)O2(OC6H40)2] 2 and (NH3CH2CH2NH2)2[W^(VI)O2(OC6H4O)2] 3, the results show that tungsten(VI) is less active in redox than molybdenum (VI) and that the change of the valence induced by substitution of W(VI) for Mo(V) in EMO2(OC6H40)2]n- does not influence the coordination geometry of the complex anion in which the metal center exhibits distorted octahedral coordination with cis-dioxo catechol. The responses to EPR of complexes 1 and 2 are active but complex 3 is silent,and the UV-vis spectra exhibited by the three complexes are obvious different because of the different electronic configuration between the central Mo(V) and W(VI) ions in the complexes.It is noteworthy that complexes 1 and 2 have the similar EPR signal to flavoenzyme, suggesting that the three complexes have the same coordination geometry feature with the co-factor of flavoenzyme. 相似文献
6.
The title compound was synthesized by reaction of Cu(ClO4)2, picolinic acid and carbamide in C2H5OH/CH3CN solution, and characterized by single-crystal X-ray diffraction. It crystallizes in the orthorhombic system, space group Pbca with a=14.0481(8), b=9.0130(5), c=18.626(1)?, V=2358.3(2)?3, Z=4, Dx=1.771g·cm-3, μ=1.235mm-1 and F(000)=1276. The final R factor is 0.0440 for 1434 observed reflections. The X-ray analysis revealed that the copper(Ⅱ) atom is coordinated by two picolinic ligands in the equatorial plane, while the two oxygen atoms of perchlorate occupy the axial positions of octahedron with lengthened Cu-O distances, resulting in a 4+2 elongated octahedral environment. In the compound, there also exist two protonated carbamide cations for charge balance. CCDC: 195354. 相似文献
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9.
Kexuan Zhang 《中国物理 B》2021,30(12):126802-126802
The interfacial enhanced ferromagnetism in maganite/ruthenate system is regarded as a promising path to broaden the potential of oxide-based electronic device applications. Here, we systematically studied the physical properties of LaLa1-xCaxMnO3/SrRuO3 superlattices and compared them with the LaLa1-xCaxMnO3 thin films and bulk compounds. The LaLa1-xCaxMnO3/SrRuO3 superlattices exhibit significant enhancement of Curie temperature (TC) beyond the corresponding thin films and bulks. Based on these results, we constructed an extended phase diagram of LaLa1-xCaxMnO3 under interfacial engineering. We considered the interfacial charge transfer and structural proximity effects as the origin of the interface-induced high TC. The structural characterizations revealed a pronounced increase of B-O-B bond angle, which could be the main driving force for the high TC in the superlattices. Our work inspires a deeper understanding of the collective effects of interfacial charge transfer and structural proximity on the physical properties of oxide heterostructures. 相似文献
10.
Jie Wang Denan Li Honggui Yang Shufan Yao Prof. Qianqian Zhu Prof. Masahiro Sadakane Prof. Yanshuo Li Prof. Wataru Ueda Prof. Zhenxin Zhang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(41):e202200618
Zeolitic octahedral metal oxides are inorganic crystalline microporous materials with adsorption and redox properties. New ϵ-Keggin nickel molybdate–based zeolitic octahedral metal oxides have been synthesized. 31P NMR spectroscopy shows that reduction of MoVI-based molybdates forms an ϵ-Keggin polyoxometalate that immediately transfers to the solid phase. Investigation of the formation process indicates that a low Ni concentration, insoluble reducing agent, and long synthesis time are the critical factors for obtaining the zeolite octahedral metal oxides rather than the ϵ-Keggin polyoxometalate molecule. The synthesized zeolitic nickel molybdate with Na+ is used as the adsorbent, which effectively separates C2 hydrocarbon mixtures. 相似文献