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61.
The structure and stability of classical and bridged C2H
3
+
is reinvestigated. The SCF and CEPA-PNO computations performed with flexibles andp basis sets including twod-sets on carbon confirm our previous results. We find the protonated acetylene structure to be more stable than the vinyl
cation by 3.5–4 kcal/mol. The energy barrier for the interconversion of these two structures is at most a few tenths of a
kcal/mol. The equilibrium SCF geometries of Weberet al. [15] are affected insignificantly by further optimization at the CEPA-PNO level.
Several structures for the interaction of C2H
3
+
with HF have been investigated at the SCF level. With our largest basis set which includes a complete set of polarization
functions we find a remarkable levelling of the stabilities of most of the structures. In these cases the stabilization energy
ΔE ranges from −10 to −13 kcal/mol. 相似文献
62.
Crespi M. S. Silva A. R. Ribeiro C. A. Oliveira S. C. Santiago-Silva M. R. 《Journal of Thermal Analysis and Calorimetry》2003,72(3):1049-1056
The thermal behavior and non-isothermal kinetics of thermal decomposition of three different kinds of composting of the USR
like: stack with drilled PVC tubes (ST), revolved stack (SR) and stack with material of structure (SM), from the usine of
composing of Araraquara city, Săo Paulo state, Brazil, within a period of 132 days of composting were studied. Results from
TG, DTG and DSC curves obtained on inert atmosphere indicated that the cellulosic fraction present, despite the slow degradation
during the composting process, is thermally less stable than other substances originated from that process. Due to that behavior,
the cellulosic fraction decomposition could be kinetically evaluated through non-isothermal methods of analysis. The values
obtained were: average activation energy, Ea=248, 257 and 259 kJ mol-1 and pre- exponential factor, logA=21.4, 22.5, 22.7 min-1, to the ST, SR and SM, respectively. From Ea and logA values and DSC curves, Málek procedure could be applied, suggesting that the SB (Šesták-Berggren) kinetic model is the appropriated
one to the first thermal decomposition step.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
63.
B. S. Narwade P. G. Gawali Rekha Pande G. M. Kalamse 《Journal of Chemical Sciences》2005,117(6):673-676
Dielectric constant (ε’) and dielectric loss (ε") of n-propyl alcohol (PA), ethylenediamine (EDA) and their binary mixtures,
for different mole fractions of ethylenediamine have been experimentally measured at 11.15 GHz microwave frequency. Values
of density (ρ), viscosity (η) and square refractive index (n
D
2
) of binary mixtures as well as those of pure liquids are reported. Excess square refractive index, viscosity and activation
energy of viscous flow have also been estimated. These parameters have been used to explain the formation of complexes in
the system. 相似文献
64.
S. Shen E. D. Sudol M. S. El-Aasser 《Journal of polymer science. Part A, Polymer chemistry》1994,32(6):1087-1100
The mechanism for the formation of micron-size polymer particles in the dispersion polymerization of methyl methacrylate was investigated by applying dynamic light scattering to monitor the evolution of the average particle size in the early stages of the polymerization. In addition, the contributions of physically adsorbed stabilizer and graft copolymer were evaluated by measuring the bound, unbound (adsorbed), and free stabilizer, and by determining the amount of added stabilizer required in seeded dispersion polymerizations. Twenty nanometer particles (termed nuclei) were the smallest particles detected and are considered to be formed by aggregation of growing polymer chains precipitating from solution as they exceed their critical chain length. Aggregation of these nuclei with themselves and their aggregates continues until mature and stable particles are formed. This occurs when sufficient stabilizer occupies the particle surface which includes both the polymeric stabilizer [poly(vinylpyrrolidone)] and its graft copolymer which is created in situ. The effects of process variables are discussed based on this mechanistic picture of the dispersion polymerization process. © 1994 John Wiley & Sons, Inc. 相似文献
65.
Thermodynamic studies were performed on 12 pairs of N-trifluoroacetyl-O-alkyl nipecotic acid ester enantiomers on diluted permethylated beta-cyclodextrin stationary phase (CP Chirasil-Dex CB). The influence of ester alkyl group structure on interaction with permethylated beta-cyclodextrin (Me-CD) and enantioselectivity was studied. The types of alkyl groups studied included n-alkyl (C1-C5) and groups containing branching at differing locations relative to the chiral center of the molecule. The results show that for a given molecular weight, the n-alkyl esters have stronger interactions with Me-CD than esters containing branched alkyl groups. However, although having weaker interactions with Me-CD, esters containing alpha-branched alkyl groups exhibit higher enantioselectivity than the corresponding n-alkyl or beta-branched isobutyl esters. From the retention data, thermodynamic parameters were estimated using the retention increment method and enthalpy-entropy compensation plots (ln R' versus deltaH) were constructed. The results suggest that ester enantiomers with branching at the alpha-carbon of the ester alkyl group have additional and/or different types of enantioselective interactions with Me-CD than the C1-C5 n-alkyl esters or beta-branched isobutyl ester. In order to obtain a qualitative sense of the interaction with Me-CD, structures of the diastereomeric complexes formed between Me-CD and some of the ester enantiomers were modeled using simulated annealing molecular dynamics. 相似文献
66.
Summary A program is described which calculates the number of effective plates and the coating efficiency over the entire range of a test chromatogram. The peak widths at half height are derived by assuming a Gaussian peak shape. The interpolated peak width at k=4 is used for computing a standardized number of effective plates. Plate height, column permeability, overall performance and a novel parameter called sampling efficiency are calculated from 5 other figures — i. e. carrier gas code, pressure drop, column length, column temperature and particle size.Dedicated to Dr. Leslie S. Ettre for his 60th birthday. 相似文献
67.
The predictive accuracy for estimating infinite dilution activity coefficients by a modification of the UNIFAC method wherein the group interaction parameters were based on only data (referred to as -based UNIFAC) has been studied. Estimates and measured values were compared for six prototypical solutes in a series of homologous n-alkanes, l-alcohols and alkanenitrile solvents. Despite the fact that the interaction parameters were derived using only data, this approach still gave serious errors due to several inherent problems in the original UNIFAC model. Its performance is sometimes even poorer than that of the original UNIFAC method. For example for nitromethane in alcohols and p-dioxane in nitriles values predicted by the -based UNIFAC are essentially zero. The large errors for these systems are most likely due to inaccurate interaction parameters in the -based UNIFAC method. 相似文献
68.
六十年代后期,在Hartree-Fock-Slater法的基础上,提出了Xα法[1].用于原子结构计算的Xα法与HF(Hartree-Fock)法的主要区别在于:用简单的统计平均交换势替代了HF法中计算最为困难的电子交换势,从而在保持较高理论严谨性和计算精确度的同时,大大减少了计算工作量,近年来获得了广泛的应用.我们尝试用经过适当修改的Xα方法,计算原子参数,解决分子结构中的某些问题.用原子参数解决分子问题,历来是化学和物理工作者常用的方法.本工作的意图是引入一个比HF法简单的容易在微机上实现的某种表现原子参数的计算方法,提供… 相似文献
69.
We calculate energy barriers of atom- and proton-transfer reactions in hydrogen-bonded complexes in the gas phase. Our calculations do not involve adjustable parameters and are based on bond-dissociation energies, ionization potentials, electron affinities, bond lengths, and vibration frequencies of the reactive bonds. The calculated barriers are in agreement with experimental data and high-level ab initio calculations. We relate the height of the barrier with the molecular properties of the reactants and complexes. The structure of complexes with strong hydrogen bonds approaches that of the transition state, and substantially reduces the barrier height. We calculate the hydrogen-abstraction rates in H-bonded systems using the transition-state theory with the semiclassical correction for tunneling, and show that they are in excellent agreement with the experimental data. H-bonding leads to an increase in tunneling corrections at room temperature. 相似文献
70.
The generalized (reductive) criterion of solvent polarity was obtained by the method of multiparametric optimization of the Snyder index P", Hildebrand parameter
T
, permittivity
r
, and solvatochromism parameter E
T
(30). Possibilities of employing this criterion for estimation of the elution power of normal and reversed mobile phases used in high-performance liquid chromatography were considered. 相似文献