首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   3215篇
  免费   590篇
  国内免费   162篇
化学   431篇
晶体学   2篇
力学   698篇
综合类   42篇
数学   1745篇
物理学   1049篇
  2025年   12篇
  2024年   40篇
  2023年   32篇
  2022年   35篇
  2021年   39篇
  2020年   83篇
  2019年   81篇
  2018年   84篇
  2017年   69篇
  2016年   77篇
  2015年   64篇
  2014年   154篇
  2013年   199篇
  2012年   130篇
  2011年   169篇
  2010年   171篇
  2009年   179篇
  2008年   194篇
  2007年   219篇
  2006年   164篇
  2005年   152篇
  2004年   166篇
  2003年   183篇
  2002年   137篇
  2001年   131篇
  2000年   125篇
  1999年   116篇
  1998年   93篇
  1997年   109篇
  1996年   79篇
  1995年   70篇
  1994年   38篇
  1993年   45篇
  1992年   62篇
  1991年   59篇
  1990年   24篇
  1989年   20篇
  1988年   17篇
  1987年   18篇
  1986年   17篇
  1985年   24篇
  1984年   13篇
  1983年   7篇
  1982年   11篇
  1981年   9篇
  1980年   5篇
  1979年   10篇
  1978年   10篇
  1977年   9篇
  1976年   4篇
排序方式: 共有3967条查询结果,搜索用时 15 毫秒
141.
Based on a partitioning of the total correlation energy into contributions from parallel‐ and antiparallel‐spin pairs of electrons, a modified third‐order Møller–Plesset (MP) perturbation theory is developed. The method, termed SCS–MP3 (SCS for spin‐component‐scaled) continues previous work on an improved version of MP2 (S. Grimme, J Chem Phys 2003, 118, 9095). A benchmark set of 32 isogyric reaction energies, 11 atomization energies, and 11 stretched geometries is used to assess to performance of the model in comparison to the standard quantum chemical approaches MP2, MP3, and QCISD(T). It is found, that the new method performs significantly better than usual MP2/MP3 and even outperforms the more costly QCISD method. Opposite to the usual MP series, the SCS third‐order correction uniformly improves the results. Dramatic enhancements are especially observed for the more difficult atomization energies, some of the stretched geometries, and reaction and ionization energies involving transition metal compounds where the method seems to be competitive or even superior to the widely used density functional approaches. Further tests performed for other complex systems (biradicals, C20 isomers, transition states) demonstrate that the SCS–MP3 model yields often results of QCISD(T) accuracy. The uniformity with which the new approach improves for very different correlation problems indicates significant robustness, and suggests it as a valuable quantum chemical method of general use. © 2003 Wiley Periodicals, Inc. J Comput Chem 24: 1529–1537, 2003  相似文献   
142.
143.
This study describes the framework of the quantum mechanical (QM)/Monte Carlo (MC)/free‐energy perturbation (FEP) method, a FEP method based on MC simulations using quantum chemical calculations. Because a series of structures generated by interpolating internal coordinates between transition state and reactant did not produce smooth free‐energy profiles, we used structures from the intrinsic reaction coordinate calculations. This method was first applied to the Diels–Alder reaction between methyl vinyl ketone and cyclopentadiene and produced ΔG values of 20.1 and 21.4 kcal mol?1 in aqueous and methanol solutions, respectively. They are very consistent with the experimentally observed values. The other two applications were the free‐energy surfaces for the Cope elimination of N,N‐dimethyl‐3‐phenylbutan‐2‐amine oxide in aqueous, dimethyl sulfoxide, and tetrahydrofuran solutions, and the Kemp decarboxylation of 6‐hydroxybenzo‐isoxazole‐3‐carboxylic acid in aqueous, dimethyl sulfoxide, and CH3CN solutions. The calculated activation free energies differed by less than 1.8 kcal mol?1 from the experimental values for these reactions. Although we used droplet models for the QM/MC/FEP simulations, the calculated results for three reactions are very close to the experimental data. It was confirmed that most of the interactions between the solute and solvents can be described using small numbers of solvent molecules. This is because a few solvent molecules can produce large portions of the solute–solvent interaction energies at the reaction centers. When we confirmed the dependency on the droplet sizes of solvents, the QM/MC/FEP for a large droplet with 106 water molecules produced a ΔG value similar to the experimental values, as well as that for a small droplet with 34 molecules. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2011  相似文献   
144.
Dimethylsulfoxide (DMSO) kaolinite complexes of low-and high-defect kaolinites were studied by thermo-IR-spectroscopy analysis. Samples were gradually heated up to 170°C, three hours at each temperature. After cooling to room temperature, they were pressed into KBr disks and their spectra were recorded. From the spectra two types of complexes were identified. In the spectrum of type I complex two bands were attributed to asymmetric and symmetric H-O-H stretching vibrations of intercalated water, bridging between DMSO and the clay-O-planes. As a result of H-bonds between intercalated water molecules and the O-planes, Si-O vibrations of the clay framework were perturbed, in the low-defect kaolinite more than in the high-defect. Type II complex was obtained by the thermal escape of the intercalated water. Consequently, the H-O-H bands were absent from the spectrum of type II complex and the Si-O bands were not perturbed. Type I complex was present up to 120°C whereas type II between 130 and 150°C. The presence of intercalated DMSO was proved from the appearance of methyl bands. These bands decreased with temperature due to the thermal evolution of DMSO but disappeared only in spectra of samples heated at 160°C. Intercalated DMSO was H-bonded to the inner-surface hydroxyls and vibrations associated with this group were perturbed. Due to the thermal evolution of DMSO the intensities of the perturbed bands decreased with the temperature. They disappeared at 160°C together with the methyl bands.  相似文献   
145.
The singularly perturbed Robin boundary value problems for the semilinear elliptic equation are considered. Under suitable conditions and by using the fixed point theorem the existence ,uniqueness and asymptotic behavior of solution for the boundary value problems are studied.  相似文献   
146.
环形截面螺旋管道内二次流动特性的研究   总被引:6,自引:0,他引:6  
张金锁  章本照 《力学学报》2001,33(2):183-194
从曲线柱坐标系下的N-S方程出发,以曲率和挠率为小参数,采用摄动法求解了环形截面螺旋管道内的黏性流动,给出了完全二阶摄动解,结果表明:当挠率为零时,二次流表现为上下对称的四个涡;当挠率不为零,涡的对称性遭到破坏,二次涡的强度和个数受De数和环形截面内外径之比δ的影响,轴向速度最大值在De数较小时靠近管道的内侧,随着De数的增加,其最大值向外侧移动。  相似文献   
147.
保守体系的微分方程可用Hamilton体系的方法描述,其特点是保辛。两个辛矩阵之和不能保辛,两个辛矩阵的乘积仍是辛矩阵。最常用的小参数摄动法用的是加法,因此对辛矩阵不能保辛。从保辛的角度,要用正则变换。本文针对非线性微分方程,运用自变量坐标变换,对原系统进行变换。由此推导出变换后系统的变分原理。引入Hamilton对偶变量,通过数学变换,得到变系数非线性方程。针对该方程,本文提出了保辛摄动算法。通过数值算例,对不同步长下,保辛摄动法、多尺度摄动法、龙格库塔法和精确解的结果做了比较。数值例题表明,对于非线性方程,本文提出的保辛摄动算法有良好的精度。在步长增大的情况下,保辛摄动保持了良好的稳定性。  相似文献   
148.
A modified shear lag analysis, taking into account the notion of stress perturbation function, is employed to evaluate the effect of transverse cracks on the stiffness reduction in [±θn/90m]S angle-ply laminated composites. Effects of number of 90° layers and number of ±θ layers on the laminate stiffness have also been studied. The present results represent well the dependence of the degradation of mechanical properties on the fibre orientation angle of the outer layers, the number of cracked cross-ply layers and the number of uncracked outer ±θ layers in the laminate.  相似文献   
149.
为精确计算舰载武器的飞行状态参数,以弹体纵向运动过程为研究对象,推导了包含误差干扰源在内的纵向扰动运动学方程,利用"系数冻结法"及拉普拉斯变换得到解析解,拟合出弹体被动段纵向运动的气动参数公式,采用三坐标雷达测量量作为系统量测方程,从而对气动参数误差干扰源进行最优估计。计算结果表明:该算法可以使俯仰操纵力矩系数导数误差的精度稳定在±0.007(°)~(-1)范围内,阻力系数误差的精度趋于±0.025之间;升力系数误差基本稳定在±0.12之间;俯仰力矩系数对攻角的导数偏差精度稳定在±0.011(°)~(-1)之间;俯仰阻尼力矩系数误差的精度收敛于±0.009(°)~(-1)之间,且算法收敛速度快,可为重构高精度的弹道参数提供支撑。  相似文献   
150.
The fundamental and subharmonic resonances of a two degree-of-freedom oscillator with cubic stiffness nonlinearities and linear viscous damping are examined using a multiple-seales averaging analysis. The system is in a 1–1 internal resonance, i.e., it has two equal linearized eigenfrequencies, and it possesses nonlinear normal modes. For weak coupling stiffnesses the internal resonance gives rise to a Hamiltonian Pitchfork bifurcation of normal modes which in turn affects the topology of the fundamental and subharmonic resonance curves. It is shown that the number of resonance branches differs before and after the mode bifurcation, and that jump phenomena are possible between forced modes. Some of the steady state solutions were found to be very sensitive to damping: a whole branch of fundamental resonances was eliminated even for small amounts of viscous damping, and subharmonic steady state solutions were shifted by damping to higher frequencies. The analytical results are verified by a numerical integration of the equations of motion, and a discussion of the effects of the mode bifurcation on the dynamics of the system is given.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号