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91.
We describe a simple strategy for calculating the cohesive energy of certain kinds of crystal using readily available quantum chemistry techniques. The strategy involves the calculation of the electron correlation energies of a hierarchy of free clusters, and the cohesive energy E(coh) is extracted from the constant of proportionality between these correlation energies and the number of atoms in the limit of large clusters. We apply the strategy to the LiH crystal, using the MP2 and CCSD(T) schemes for the correlation energy, and show that for this material E(coh) can be obtained to an accuracy of approximately 30 meV per ion pair. Comparison with the experimental value, after correction for zero-point energy, confirms this accuracy. 相似文献
92.
The purpose of this work is to understand the effect of an external environment on the adiabatic dynamics of a quantum critical system. By means of scaling arguments we derive a general expression for the density of excitations produced in the quench as a function of its velocity and of the temperature of the bath. We corroborate the scaling analysis by explicitly solving the case of a one-dimensional quantum Ising model coupled to an Ohmic bath. 相似文献
93.
Saul F. Teloxa Stuart C. D. Kennington Marc Camats Prof. Pedro Romea Prof. Fèlix Urpí Prof. Gabriel Aullón Dr. Mercè Font-Bardia 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(50):11540-11548
A direct and highly enantioselective reaction of N-azidoacetyl-1,3-thiazolidine-2-thione with trimethyl orthoformate catalyzed by Tol-BINAPNiCl2 in the presence of TESOTf and 2,6-lutidine is reported. The heterocyclic scaffold can be easily removed by addition of a wide array of amines to give the corresponding enantiomerically pure 2-azido-3,3-dimethoxypropanamides in high yields. Appropriate manipulation of the N-benzyl amide derivative provides an efficient access to the antiepileptic agent lacosamide through a new enantioselective C−C bond-forming process. DFT computational studies uncover clues for the understanding of the remarkable stereocontrol of the addition of a nickel(II) enolate to a putative oxocarbenium intermediate from trimethyl orthoformate. 相似文献
94.
95.
Deumal M Bearpark MJ Robb MA Pontillon Y Novoa JJ 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(24):6422-6432
The mechanism of magnetic interactions in the bulk ferromagnet para-(methylthio)phenyl nitronyl nitroxide crystal (YUJNEW) has been theoretically reinvestigated, using only data from ab initio calculations and avoiding any a priori assumptions. We first calculate the microscopic magnetic interactions (JAB exchange couplings) between all unique radical pairs in the crystal, and then generate the macroscopic magnetic properties from the energy levels of the corresponding Heisenberg Hamiltonian. We thus propose a first principles, bottom-up (i.e. micro-to-macro) approach that brings theory and experiment together. We have applied this strategy to study the magnetism of YUJNEW using data from the previously reported 298 and 114 K crystal structures, and also data from a 10 K neutron diffraction structure fully reported in this work. The magnetic topology at 298 K is two-dimensional: noninteracting planes, with three different in-plane JAB pair interactions (+0.24, +0.09, and -0.11 cm(-1)) and one numerically negligible (+0.02 cm(-1)) inter-plane JAB interaction. In contrast, the magnetic topology at 114 and 10 K is three-dimensional, with two non-negligible in-plane JAB constants (+0.11 and +0.07 cm(-1) at 114 K; +0.22 and +0.07 cm(-1) at 10 K) and one inter-plane pair interaction (+0.07 cm(-1) at 114 K; +0.08 cm(-1) at 10 K). Although this three-dimensional magnetic topology is consistent with YUJNEW being a bulk ferromagnet, there is only a qualitative agreement between computed and experimental magnetic susceptibility chiT(T) data at 114 K. However, the experimental chiT(T) curve is quantitatively reproduced at 10 K. The heat capacity curve presents a peak at around 0.12 K, close to the estimated experimental peak (0.20 K). 相似文献
96.
Monfort M Resino I Ribas J Solans X Font-Bardia M Rabu P Drillon M 《Inorganic chemistry》2000,39(12):2572-2576
Two new one-dimensional nickel(II) complexes were synthesized and characterized: [Ni(N,N-dimethylethylenediamine)(N3)2] (1) and [Ni(2-aminoethylpyridine)(N3)2] (2). The crystal structures of 1 and 2 were solved. Complex 1 crystallizes in the monoclinic system, space group P2(1)/n with a = 10.569(2) A, b = 7.331(4) A, c = 12.9072(8) A, beta = 111.324(10) degrees, and Z = 4. Complex 2 crystallizes in the monoclinic system, space group P2(1)/c with a = 12.299(5) A, b = 14.307(2) A, c = 12.604(3), beta = 106.72(2) degrees, and Z = 4. The two complexes are similar and may be described as one-dimensional systems with double-azido-bridged ligands in end-to-end and end-on coordination alternatively. The end-on moiety is almost identical for 1 and 2, but the end-to-end moiety is different in each structure: for 1 this part is almost planar but for 2 is nonplanar. In both cases the Ni atoms are situated in similar distorted octahedral environments. The magnetic properties of the two compounds were studied by susceptibility measurements vs temperature. The chi M vs T plots for 1 and 2 show a global antiferromagnetic behavior with a maximum near room temperature for 1 and at very low temperature for 2. J values for 1 and 2 were deduced from the spin Hamiltonian -sigma(J1SiSi+1 + J2Si+1Si+2). The computational method was based on the numerical solution for finite systems of increasing size. J values for 1 were J1 = -187 cm-1 and J2 = +77 cm-1 and for 2 J1 = -28 cm-1 and J2 = +73 cm-1. The positive values correspond to end-on azido ligands and the negative values to end-to-end azido ligands. Since the geometries of the [Ni(N3)]2 moieties involving the end-on azido ligands are almost the same in the two structures, the ferromagnetic coupling is nearly identical in the two compounds, while the significantly different antiferromagnetic couplings reflect the near planarity of the end-to-end Ni2(N3)2 fragment in 1 and its twisted geometry in 2. 相似文献
97.
Larrosa I Romea P Urpí F Balsells D Vilarrasa J Font-Bardia M Solans X 《Organic letters》2002,4(26):4651-4654
[reaction: see text] Lewis acid mediated addition of chiral titanium enolates to glycals provides either alpha- or beta-1'-methyl-substituted C-glycosides. This highly stereoselective methodology permits the modular preparation of three of the four possible diastereomers. 相似文献
98.
Mazzanti A Calbet T Font-Bardia M Moyano A Rios R 《Organic & biomolecular chemistry》2012,10(8):1645-1652
The enantioselective synthesis of pyrazol-3-ones has not been extensively studied in organic synthesis. Here in we report the first asymmetric addition of pyrazolones to maleimides catalyzed by bifunctional thiourea catalysts. 相似文献
99.
Bernardi L Cerè V Femoni C Pollicino S Ricci A 《The Journal of organic chemistry》2003,68(8):3348-3351
Oxime ethers derived from 2-pyridinecarboxaldehyde and glyoxylic acid can be effectively allylated in water with five differently functionalized allylic bromides promoted by indium. When the metal is positioned in close proximity of flanking heteroatomic centers, chelation by In is indeed operative and affects both reactivity and stereochemistry. Stereochemical assignments in the addition products were based on X-ray crystallographic measurements and spectral correlations. 相似文献
100.
Scolaro LM Romeo A Castriciano MA De Luca G Patanè S Micali N 《Journal of the American Chemical Society》2003,125(8):2040-2041
Simple irradiation by UV light of porphyrin TpyP and its zinc(II) and manganese(III) metal derivatives in chlorinated solvents leads to the deposition on silica of mesoscale aggregates. The process is due to the photochemical decomposition of the solvent with generation of HCl, which causes the precipitation of a protonated form. The morphology of the resulting objects is driven by the nature of the inserted metal ion. 相似文献