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31.
Margiolaki I Margadonna S Prassides K Hansen T Ishii K Suematsu H 《Journal of the American Chemical Society》2002,124(38):11288-11289
The powder neutron diffraction technique has been used for the direct observation of magnetic scattering below a Curie temperature of approximately 14 K in the fullerene-based molecular ferromagnet Eu6C60. Europium is in the divalent state with a magnetic moment of 7.1(3) muB per atom, and the configurational symmetry of the magnetic structure is body-centered cubic. Close contacts between Eu2+ and neighboring C60 units provide the signature of orbital hybridization, which can evidently account for the conducting and magnetic properties of the material. 相似文献
32.
Balek V. Málek Z. Šubrt J. Guglielmi M. Innozenzi P. Rigato V. Della Mea G. 《Journal of Thermal Analysis and Calorimetry》2004,76(1):43-48
Emanation Thermal Analysis (ETA) was demonstrated as a tool for the characterization of microstructure changes of a sol-gel
precursor for silica-titania layers deposited on the glass plate to be used as planar waveguides. Temperature ranges of 280-330
and 380-500°C, respectively, in which the densification of the layers took place, were determined by ETA under in situ conditions
of the sample heating. Results of thermogravimetry were compared with the ETA data.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
33.
Michèle Decouzon Jean-Fraçois Gal Jérôme Gayraud Pierre-Charles Maria Gian-Angelo Vaglio Paolo Volpe 《Journal of the American Society for Mass Spectrometry》1993,4(1):54-57
An accurate gas-phase acidity for germane (enthalpy scale, equivalent to the proton affinity of GeH3 ?), ΔH acid o(GeH4) = 1502.0 ± 5.1 kJ mol?1, is obtained by constructing a consistent acidity ladder between GeH4, and H2S by using Fourier transform-ion cyclotron resonance spectrometry, and 0 and 298.15 K values for the first bond dissociation energy of GeH4 are proposed: D0 o(H3Ge-H) = 352 ± 9 kJ mol?1; D o(H3Ge-H) = 358 ± 9 kJ mol?1, respectively. These results are compared with experimental and theoretical data reported in the literature. Methylgermane was found to be a weaker acid than germane by approximately 35 kJ mol?1: ΔH acid o = 1536.6 kJ mol?1. 相似文献
34.
L. Stievano S. Calogero R. Psaro M. Guidotti R. Della Pergola F. E. Wagner 《Journal of Cluster Science》2001,12(1):123-137
193Ir and 57Fe Mössbauer spectroscopy was used to investigate the structure of the [Fe2Ir2(CO)12]2- cluster compound and the adsorption of this cluster on hydrated MgO. Supported samples were prepared by impregnation of the magnesia with solutions of [Et4N]2[Fe2Ir2(CO)12] in acetone. The Mössbauer and FT-IR spectra of the MgO-supported cluster confirm that the bimetallic carbonyl is molecularly physisorbed onto MgO without undergoing any transformation or decomposition. The easy solvent extraction of the intact cluster from the oxide surface excludes ion pairing between the cluster anion and the Mg2+ surface sites. Mössbauer spectra are in agreement with the refined structure of the molecular cluster and the temperature dependence of the 57Fe Mössbauer spectra above 80 K is consistent with the low degree of interaction of the cluster with the support. This technique, therefore, appears to be promising in order to infer structural information when X-ray determination fails. 相似文献
35.
S. Della Negra H. Gauvin H. Jungclas Y. Le Beyec M. Lefort 《Zeitschrift für Physik A Hadrons and Nuclei》1977,282(1):65-73
Excitation functions have been drawn for evaporation residues issued from150Gd, a compound nucleus produced either by16O ions on134Ba, or by40Ar on110Pd. Absolute cross sections were measured for145–147Gd,145–147Eu,141m Sm,143m Sm,140m Pm and139m Nd. Complete fusion cross sections have been obtained and compared to calculated estimations based, at low energies, on the simple expressionσ CF=πR Fuss 2 (1?V Fus/E) whereR Fus andV Fus are respectively the distance and the potential for fusion atdV/dr=0. For high energies σCF=πR cr 2 (1?Vcr/E) with the model of critical distanceR cr and critical potentialV cr. Thresholds energies have been determined with a particular care. The analysis of the shape and the width of excitation functions, particularly for the emission of 4 and 5 neutrons, has been carried out and compared to calculated values. The difference between argon and oxygen induced reactions has been attributed to the difference inl population in the entrance channel. 相似文献
36.
Gian Angelo Vaglio Paolo Volpe Lorenza Operti 《Journal of mass spectrometry : JMS》1982,17(12):617-619
The negative ion chemical ionization mass spectra, with ammonia and methane as reagent gases, of the (η6-arene)Cr(CO)3 complexes, where the arene is C6H5COCH3, C6H5COC2H5, C6H5COC3H7, C6H5COC(CH3)3, 2-CH3C6H4COC3H7, C6H5COOCH3, C6H5CH3, 1,3,5-(CH3)3C6H3 and C6H5CH2COC2H5, are reported. Similar behaviour is observed with the two reagent gases, but ammonia shows a much higher abundance for the ions produced by reactions of [NH2]? with sample molecules. The compounds containing the C6H5CO group display an abundant [M]? ˙, whereas the other compounds exhibit [M? H]? as base peak, produced by ion/molecule reactions. A comparison of the negative ion chemical ionization mass spectra of the (η6-arene)Cr(CO)3 complexes with those of the corresponding ligands shows the strong electron withdrawing power of the Cr(CO)3 group in the gas phase. 相似文献
37.
Molar enthalpies of solution at infinite dilution have been determined at 25°C for several N-alkyl and N,N-dialkylamides in water and in carbon tetrachloride, using a Calvet-type rotating calorimeter, and solution concentrations below 5×10–2 molal. Relevant enthalpies of transfer between the two solvents also have been derived. Molar enthalpies of solvation have been obtained by adding enthalpies of vaporization to solution values. Results are compared with those of other laboratories on other substituted amides, and their dependence on the number of carbon atoms in the chain is discussed. A possible computation of solvation enthalpies of functional groups is suggested and results for hydration of peptide or similar groups present in the compounds examined are discussed in terms of current models of their hydration and hydrogen bond formation.Presented at the sixth Italian meeting on Calorimetry and Thermal Analysis (AICAT) held in Naples, December 4–7, 1984. 相似文献
38.
An effective exact-exchange Kohn-Sham approach for the treatment of excited electronic states, the generalized adiabatic connection open-shell localized Hartree-Fock (GAC-OSLHF) method is presented. The GAC-OSLHF method is based on the generalized adiabatic connection Kohn-Sham formalism and therefore capable of treating excited electronic states, which are not the energetically lowest of their symmetry. The method is self-interaction free and allows for a fully self-consistent computation of excited valence as well as Rydberg states. Results for atoms and small- and medium-size molecules are presented and compared to restricted open-shell Hartree-Fock (ROHF) and time-dependent density-functional results as well as to experimental data. While GAC-OSLHF and ROHF results are quite close to each other, the GAC-OSLHF method shows a much better convergence behavior. Moreover, the GAC-OSLHF method as a Kohn-Sham method, in contrast to the ROHF approach, represents a framework which allows also for a treatment of correlation besides an exchange by appropriate functionals. In contrast to the common time-dependent density-functional methods, the GAC-OSLHF approach is capable of treating doubly or multiply excited states and can be easily applied to molecules with an open-shell ground state. On the nodal planes of the energetically highest occupied orbital, the local multiplicative GAC-OSLHF exchange potential asymptotically approaches a different, i.e., nonzero, value than in other regions, an asymptotic behavior which is known from exact Kohn-Sham exchange potentials of ground states of molecules. 相似文献
39.
Leibold C Alvarez RM Cutin EH Della Vedova CO Oberhammer H 《Inorganic chemistry》2003,42(13):4071-4075
The IR (gas) and Raman (liquid) spectra of FC(O)NSCl(2) demonstrate the presence of a conformational mixture in both phases. According to a gas electron diffraction study, the main conformer (94(8)%) possesses a syn-syn structure (C(O)F group synperiplanar with respect to the SCl(2) bisector and the C=O bond synperiplanar to the N=S bond). Quantum chemical calculations (HF, B3LYP and MP2 with 6-31G basis set, and MP2/6-311(2df)) predict a syn-anti structure for the second conformer. Analysis of the IR (gas) spectrum results in a contribution of 5(1)% of the minor form, corresponding to a Gibbs free energy difference DeltaG degrees = G degrees (syn-anti) - G degrees (syn-syn) = 1.75(15) kcal/mol. This value is reproduced very well by quantum chemical calculations, which include electron correlation effects (DeltaG degrees = 1.28-1.56 kcal/mol). The HF approximation overestimates this energy difference (DeltaG degrees = 3.24 kcal/mol). 相似文献
40.
The new compound trifluoroacetylsulfenyl trifluoroacetate, CF(3)C(O)SOC(O)CF(3), which possesses two identical carbonyl substituents attached to the S-O bond, has been synthesized. The IR and UV spectra of the gas phase as well as the (13)C NMR spectrum of the solution in CDCl(3) were recorded and assigned. Quantum chemical calculations were performed with the ab initio methods HF and MP2 and the density functional approach B3LYP. The 6-31G basis set was chosen in all calculations. The molecule possesses a skew structure, and according to all computational methods, the syn-syn structure (C=O bonds of both C(O)CF(3) groups synperiplanar to S-O bond) represents the most stable conformer. In agreement with the quantum chemical calculations, the presence of small amounts (< or =5%) of a second conformer (anti-syn) cannot be excluded on the basis of the IR spectrum. The calculated values for the torsional angle around the S-O bond (delta(C-S-O-C)) of the syn-syn form are smaller than 80 degrees (72-78 degrees). Comparison with theoretical results for the corresponding disulfide CF(3)C(O)SSC(O)CF(3) and peroxide CF(3)C(O)OOC(O)CF(3) indicates that the structural properties of sulfenyl compounds are more similar to those of disulfides than to those of peroxides. 相似文献