全文获取类型
收费全文 | 3104篇 |
免费 | 92篇 |
国内免费 | 642篇 |
专业分类
化学 | 1559篇 |
晶体学 | 7篇 |
力学 | 20篇 |
综合类 | 2篇 |
数学 | 22篇 |
物理学 | 2228篇 |
出版年
2024年 | 14篇 |
2023年 | 59篇 |
2022年 | 46篇 |
2021年 | 49篇 |
2020年 | 83篇 |
2019年 | 72篇 |
2018年 | 93篇 |
2017年 | 77篇 |
2016年 | 118篇 |
2015年 | 124篇 |
2014年 | 136篇 |
2013年 | 184篇 |
2012年 | 234篇 |
2011年 | 362篇 |
2010年 | 203篇 |
2009年 | 248篇 |
2008年 | 228篇 |
2007年 | 227篇 |
2006年 | 200篇 |
2005年 | 128篇 |
2004年 | 114篇 |
2003年 | 119篇 |
2002年 | 122篇 |
2001年 | 96篇 |
2000年 | 71篇 |
1999年 | 56篇 |
1998年 | 62篇 |
1997年 | 36篇 |
1996年 | 31篇 |
1995年 | 36篇 |
1994年 | 27篇 |
1993年 | 24篇 |
1992年 | 25篇 |
1991年 | 34篇 |
1990年 | 12篇 |
1989年 | 12篇 |
1988年 | 7篇 |
1987年 | 12篇 |
1986年 | 4篇 |
1985年 | 10篇 |
1984年 | 6篇 |
1983年 | 5篇 |
1982年 | 9篇 |
1981年 | 6篇 |
1980年 | 3篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1976年 | 1篇 |
1974年 | 3篇 |
1973年 | 5篇 |
排序方式: 共有3838条查询结果,搜索用时 15 毫秒
81.
C40异构体的结构和稳定性的理论研究 总被引:1,自引:0,他引:1
利用Gaussian98程序,采用密度泛函(DFT)方法中的B3LYP,选用6-31G基组对富勒烯(Fullerene)C40的6种异构体[D5d,Td,D2h,C3v,D2(Ⅰ),D2(Ⅱ)]进行了几何构型优化,其中,对于Td对称性的C40由于易发生Jahn-Teller畸变,则降低其对称性为D2d,再进行优化.对它们的平衡几何和电子结构进行了比较具体的分析,同时,根据计算得到的总能量推断出这6种异构体的稳定性顺序是D2(Ⅰ)>D5d>Td>C3v>D2h>D2(Ⅱ). 相似文献
82.
Chemical Bonding and Pressure‐Induced Change of the Electron Configuration of Ytterbium in β‐YbAgGa2
Ulrich Schwarz Marcus Schmidt Roman Gumeniuk Walter Schnelle Michael Hanfland Konstantin Klementiev Yuri Grin 《无机化学与普通化学杂志》2004,630(1):122-126
Single‐phase polycrystalline samples of the intermetallic compound β‐YbAgGa2 were synthesized by inductive heating and subsequent annealing for eight weeks at 670 K. Magnetic properties were characterized by susceptibility measurements and indicated intermediate valence of ytterbium at ambient pressure. Angle‐dispersive X‐ray powder diffraction data of orthorhombic β‐YbAgGa2 indicate stability of the phase in the investigated pressure range from 0.1 MPa (ambient pressure) to 19 GPa. The pressure‐induced volume decrease is accompanied by an increase of the effective valence from 2.17 at ambient conditions to 2.71 at 16 GPa as evaluated by X‐ray absorption spectroscopy at the Yb LIII threshold. Analysis of the chemical bonding in β‐YbAgGa2 by integrating the electron density of the polyanion in basins as defined by the electron localization function results in an electron count Yb2.7+[(Ag0.2—)(Ga1(3b)1.0—)(Ga2(4b)1.5—)]. This finding is close to the expected values calculated by means of the Zintl rules and fits well the results of magnetic susceptibility measurements and XAS investigations. 相似文献
83.
Summary The electronically excited states of formaldehyde are examined by means of multiconfigurational second-order perturbation (CASPT2) theory with extended ANO-type basis sets. The calculations comprised five valence excited states plus all singlet 3s, 3p, and 3d members of the Rydberg series converging on the first ionization. The computed vertical excitation energies were found to be within 0.2 eV of the available experimental energies. Full geometry optimization has been performed for five valence excited states. Assuming a planar geometry, the 0-0 transition for the valence1A1( *) state is calculated to appear near 7.9 eV, close to the (n
y
3p) region. This state is, however, not planar and the true adiabatic energy is 7.4 eV, which is 2.3 eV below the corresponding vertical transition. 相似文献
84.
Ab initio calculations were performed on 18 fluorinated and unfluorinated alcohols at the B3LYP and HF levels with the 6-311G∗∗ basis set. Molar volumes of the alcohols were computed at each level and averaged to produce a scale of relative size. From this, various isosteric replacements of potential use in drug design were suggested: ethyl by FCH2CH2 or HCF2CH2, propyl by CF3CH2, isopropyl by CF3(CH3)CH or (FCH2)2CH, isobutyl or t-butyl by (CF3)2CH, and 3-methyl-2-butyl by CF3(CH3)2C. Calculation of the charge on oxygen and the Wiberg index of the CO bond allowed an electronegativity scale to be constructed for the fluoroalkyl groups. Electronegativity decreased in the order: (CF3)3C>(CF3)2CH>C2F5CH2>CF3CH2>CH3(CF3)2C>HCF2CH2>CF3(CH3)CH>(FCH2)2CH>FCH2CH2>CF3(CH3)2C. This ranking agreed with literature acid dissociation data for the alcohols studied. 相似文献
85.
Philip L. Wylie Richard J. Phillips Kenneth J. Klein Michael Q. Thompson Bruce W. Hermann 《Journal of separation science》1991,14(10):649-655
An experimental injection port has been designed for split or splitless sample introduction in capillary gas chromatography; the inlet uses electronic pressure control, in order that the column head pressure may be set from the GC keyboard, and the inlet may be used in the constant flow or constant pressure modes. Alternatively, the column head pressure may be programmed up or down during a GC run in a manner analogous to even temperature programming. Using electronic pressure control, a method was developed which used high column head pressures (high column flow rates) at the time of injection, followed by rapid reduction of the pressure to that required for optimum GC separation. In this way, high flow rates could be used at the time of splitless injection to reduce sample discrimination, while lower flow rates could be used for the separation. Using this method, up to 5 μl of a test sample could be injected in the splitless mode with no discrimination; in another experiment, 2.3 times as much sample was introduced into the column by using electronic pressure programming. Some GC peak broadening was observed in the first experiment. 相似文献
86.
Tarek M. El-Gogary Mostafa A. Diab Shreen F. El-Tantawy 《Monatshefte für Chemie / Chemical Monthly》2006,137(8):1027-1042
Summary. Equilibrium constants and molar extinction coefficients for 1:1 charge-transfer complexes between 2-hydroxyaniline (HA), 5-chloro-2-hydroxyaniline (CHA), and 4-bromo-2,6-dimethylaniline (BMA) as donors and iodine, as a typical σ-acceptor were determined spectrophotometrically in chloroform, dichloromethane, and
carbontetrachloride solutions. Spectral characteristics and formation constants are discussed in terms of donor molecular
structure and solvent polarity. The stoichiometry of the complexes was established to be 1:1. For this purpose, optical data
were subjected to the form of the Rose-Drago equation for 1:1 equilibria. Electronic absorption spectra of the studied anilines were measured in different solvents. Spectral
data were reported and band maxima were assigned to the appropriate molecular orbital transitions (π–π* and n–π* electronic transition). Solvent effects on the electronic transitions were discussed. Optimized geometry of the studied anilines
was obtained at B3LYP/6-31 + G(d). The effect of the electronic factors of the substituents on the geometrical parameters
of the ring has been explored. Geometrical values of the ring deviate from the regular hexagonal ring. Intramolecular H-bonds
in HA and CHA have been computed at B3LYP/6-31 + G(d) and MP2/6-31 + G(d) levels. The H-bonding distance was calculated to be 2.105 ? in
HA and 2.127 ? in CHA.
Abstracted from her M.Sc. thesis 相似文献
87.
利用双光束电子散斑干涉法(ESPI)对试件受热变形进行了实时观测,针对一次实验过程中得到的图片较多(300~500幅)的特点,在图像处理时摒弃了以往的手动识别等位移线的办法,用MATLAB语言编写了批处理程序,能够在采集的大量散斑图片中自动快速准确地标定等位移线,得到相应的位移和应变,并结合实时测量的温度值,获得了45钢和LY12铝合金在不同温升率下的热膨胀系数及其随温度的变化。实验结果表明,在涉及的温升率范围内,温升率的改变对材料热膨胀系数的影响不明显,材料的热膨胀系数随温度的升高略有上升。 相似文献
88.
Dispersion-corrected density functional theory method was performed to report on a high-performance adsorbent for removal of CO2 from the precombustion and natural gases. At first, the effect of Al atom impurity on the structural and electronic properties of B80 fullerene is studied. Then, the adsorption geometries and energies of gases (H2, CH4, or CO2) on the B80 and AlB79 (amphoteric adsorbents) are explored. The Al atom enhances reactivity of the cage toward the gases and the adsorption processes are more exothermic with low and high energy barriers for chemisorption of H2 and CO2, respectively. Stable chemisorption of CO2 on the AlB79 is validated by the high adsorption energy and large charge transfer, while the CH4 is just physically adsorbed on the AlB79. Further, the physisorbed gases can enhance field emission current of the AlB79 and in the continuous capturing of the gases, the magnetic moment of the cage is quenched. Furthermore, dependency of the electronic structure of the adsorbent on the gas adsorption is intensively studied. We suggest that the AlB79 could be a promising material for capture, storage, and separation of the gases and as a novel material for sustainable energy and sweetening process in the petroleum industry. 相似文献
89.
V.I. Val'kov А.V. Golovchan D.V. Varyukhin V.I. Mitsiuk V.M. Ryzhkovskii 《Journal of magnetism and magnetic materials》2012
An analysis is presented of experimental and theoretical results of the MnFeAsyP1−y (0.15≤y≤0.66) and Mn2−xFexAs0.5P0.5 (0.5≤x≤1.0) systems to identify main traits that underlie the mechanism of formation of different antiferromagnetic (AF) phases in the two systems. The discrepancy between the calculated from first principles and experimental values of the magnetic moment in the ferromagnetic phase with cation substitution in the system Mn2−xFexAs0.5P0.5 is due to the appearance of a canted magnetic structure. In this case, the emergence of an AF phase with decreasing iron concentration precedes a significant change in the electronic d-band filling. In the model of the spiral structure in the system of itinerant electrons it is shown that the stabilization of the AF phase with decreasing arsenic concentration, while maintaining the number of d-electrons, is a consequence of changes in the shape of the density of electronic states that occur with a decrease in unit-cell volume. 相似文献
90.
H. DagistanliR.H. Mutlu 《Radiation Physics and Chemistry》2012,81(3):240-241
The occupation numbers of the 3d transition metals are calculated as a function of pressure by means of the linear muffin-tin-orbital method. This data is used with the multiconfiguration Dirac-Fock (MCDF) X-ray intensity ratios (R) to estimate the variation of the intensity ratios of 3d metals with pressure. It is found that R decreases with pressure for the early 3d metals whereas it increases for the heavier 3d transition metals. 相似文献