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61.
Genre C Jeanneau E Bousseksou A Luneau D Borshch SA Matouzenko GS 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(2):697-705
We report here on the synthesis and characterisation of a first iron(II) spin-crossover coordination polymer with the dca spacer ligand, having the formula [Fe(aqin)2(dca)]ClO4.MeOH (aqin=8-aminoquinoline, dca=dicyanamide), which displays a two-step complete spin transition. Variable-temperature magnetic susceptibility measurements and M?ssbauer spectroscopy have revealed that the two relatively gradual steps are centred at 215 and 186 K and are separated by an inflection point at about 201 K, at which 50 % of the complex molecules undergo a spin transition. The two steps are related to the existence of two crystallographically inequivalent metal sites, as confirmed by the structural and M?ssbauer studies. The crystal structure was resolved at 293 K (HS form) and 130 K (LS form). Both spin-state structures belong to the triclinic P1 space group (Z=2). The complex assumes a linear chain structure, in which the active iron(II) sites are linked to each other by anionic dicyanamide ligands acting as chemical bridges. The Fe-Fe distances through the dca ligand are 8.119(1) and 7.835(1) A in the high-spin and low-spin structures, respectively. The polymeric chains extend along a (1, 0, -1) axis and are packed in sheets, between which the perchlorate anions and methanol molecules are inserted. The complex molecules are linked together by pi-stacking interactions and H-bonding between the H-donor aqin ligands and the perchlorate ions. These structural features provide a basis for cooperative interactions in the crystal lattice. Analysis of the two-step spin-crossover character in this compound suggests that covalent interactions through the spacer ligand do not provide the main mechanism of cooperativity. 相似文献
62.
We pose the problem on free harmonic bending vibrations of an infinite rotating tubular elastic rod with an internal fluid flow, prestressed by a torque and a longitudinal force. We show that these vibrations can only be realized as traveling circular helical waves. It is shown that, for any wavelength, there exist four waves, two having the form of a left-handed helix and the other two having the form of a right-handed helix. Each of these waves propagates in the positive and negative directions of the longitudinal rod axis at different velocities. These phenomena can manifest themselves in deep-hole drill columns. 相似文献
63.
The TDDFT method is first applied in a series of tetra-nuclear transition metal clusters studies for nonlinear optical properties. The results indicate that the charge transfer inside the metal core [MCu3X4] (M=W, Mo; X=S, O, Cl, Se, Br) makes contribution to the optical nonlinearity. It is possible to enhance the hyperpolarizability by substituting the ligands of the clusters. 相似文献
64.
Based on combined DFT/broken symmetry approach, a theoretical analysis of the exchange interactions in the VO(HPO(4)).0.5H(2)O solid is performed. Depending on the crystallographic structures reported in the literature, two very different spin models are formulated. In addition, a complete fit of the temperature-dependent (31)P NMR chemical shift is performed to determine exchange and hyperfine constants. The magnetic models used in the fit are those obtained by our theoretical calculations. The comparison between the calculated and fitted exchange constants confirms the adequacy of an isolated dimer model and rules out the alternating antiferromagnetic chain model for VO(HPO(4)).0.5H(2)O. 相似文献
65.
The optimized spatial structure and calculated electronic spectra of anionic clusters HfSi n ? (n = 6–20) are presented. The calculations have been performed by the density functional theory method. By comparing the calculated and available experimental data, the spatial structures of the clusters detected in the experiment have been determined. It has been established that the formation of endohedral structures begins with n = 12, when a stable structure of a prism encapsulating a hafnium atom is formed. Clusters with n = 12 and 16 have increased stability and are basic for the construction of clusters with a close number of silicon atoms. 相似文献
66.
67.
A new method for the synthesis of catalysts on polymetallic supports via the formation of intermetallic (aluminide) layer on the support surface followed by leaching and stabilization of the layer has been proposed. The intermetallic layer structure and distribution of elements in the layer were studied by scanning electron microscope considering a nickel chromium stainless-steel grid as an example. The morphology and elemental composition of the active phase on the catalyst surface were studied. The complex structure of this phase was found to consist of two types of entities with different composition located on the continuous highly porous substrate. The catalyst sample was tested in deep oxidation of CO and propane and demonstrated high activity. The developed method can be used to obtain new high-performance polymetallic catalysts. 相似文献
68.
Guillon T Salmon L Molnár G Zein S Borshch S Bousseksou A 《The journal of physical chemistry. A》2007,111(33):8223-8228
A quantum chemical study of the Fe[5-NO2-sal-(1,4,7,10)] ((1,10-bis(5-nitrosalicylaldehyde)-1,4,7,10-tetra-ezdecane-O,O',N,N',N' ',N' ')iron(II)) molecule was performed using density functional theory (DFT). Starting from the different X-ray crystallographic structures, geometry optimizations have been performed. These calculations confirmed the conformational isomerism of this complex in each spin states of the molecule ((1)A(1g) and (5)T(2g)). Each employed DFT method (B3LYP, B3LYP*, BP86, HCTH407) reproduced correctly the structural differences between the two calculated conformers when compared to the experimental structures. Furthermore, electronic polarizabilities have been calculated in each spin state and for each conformer. These calculations revealed a higher polarizability in the singlet state in agreement with the measured higher dielectric constant in this state. 相似文献
69.
70.
Institute of Chemistry, Academy of Sciences of the Moldavian SSR. Translated from Zhurnal Strukturnoi Khimii, Vol. 32, No 1, pp. 44–48, January–February, 1991. 相似文献