全文获取类型
收费全文 | 6636篇 |
免费 | 1179篇 |
国内免费 | 1073篇 |
专业分类
化学 | 3320篇 |
晶体学 | 35篇 |
力学 | 492篇 |
综合类 | 75篇 |
数学 | 1064篇 |
物理学 | 3902篇 |
出版年
2024年 | 6篇 |
2023年 | 81篇 |
2022年 | 135篇 |
2021年 | 175篇 |
2020年 | 253篇 |
2019年 | 220篇 |
2018年 | 192篇 |
2017年 | 202篇 |
2016年 | 225篇 |
2015年 | 220篇 |
2014年 | 313篇 |
2013年 | 589篇 |
2012年 | 409篇 |
2011年 | 410篇 |
2010年 | 334篇 |
2009年 | 419篇 |
2008年 | 468篇 |
2007年 | 466篇 |
2006年 | 462篇 |
2005年 | 400篇 |
2004年 | 368篇 |
2003年 | 333篇 |
2002年 | 294篇 |
2001年 | 230篇 |
2000年 | 238篇 |
1999年 | 202篇 |
1998年 | 196篇 |
1997年 | 168篇 |
1996年 | 109篇 |
1995年 | 102篇 |
1994年 | 87篇 |
1993年 | 76篇 |
1992年 | 80篇 |
1991年 | 63篇 |
1990年 | 48篇 |
1989年 | 41篇 |
1988年 | 39篇 |
1987年 | 33篇 |
1986年 | 30篇 |
1985年 | 27篇 |
1984年 | 12篇 |
1983年 | 12篇 |
1982年 | 26篇 |
1981年 | 21篇 |
1980年 | 16篇 |
1979年 | 11篇 |
1978年 | 13篇 |
1977年 | 12篇 |
1976年 | 8篇 |
1973年 | 4篇 |
排序方式: 共有8888条查询结果,搜索用时 31 毫秒
101.
胺、醇、醚类化合物电离能的自相关拓扑研究 总被引:1,自引:3,他引:1
原子的染色序数 fi 定义为 :fi=gi·xi,式中 gi 为原子i在分子中的序数 ,xi 为其染色系数 .基于fi 建立改进的原子序数自相关拓扑指数mF ,其中的1F对烷烃及其衍生物具有良好的结构选择性 .使用第一电离能 (Ip)与0 F ,1F的数量关系模型对 32种脂肪族胺、醇、醚进行估算、预测 ,结果令人满意 相似文献
102.
V. Chaplain M. L. Janex F. Lafuma C. Graillat R. Audebert 《Colloid and polymer science》1995,273(10):984-993
Studies of the adsorption of high molecular weight polymers on colloidal latex and silica particles and their subsequent flocculation were carried out. Neutral polyethylene oxide samples with both a narrow and a broad molecular weight distribution were used together with low charged cationic copolymers. The influence of the particle concentration and polymer dose on the flocculation were systematically investigated under quiescent conditions.Equilibrium bridging only occurred with polyelectrolyte, even in very dilute suspensions, at high particle coverage. In contrast to this, non-equilibrium bridging occurred with both neutral polymer and polyelectrolytes but only for more concentrated suspensions and small amounts of adsorbed polymer. Polymer adsorption in dilute suspensions, which did not show particle aggregation was measured an electrophoretic technique. In more concentrated suspensions, where flocculation takes place, we found that aggregation prevents further polymer adsorption and induces both an excluded volume and a surface effect. The consequences on the shape of the isotherms differ according to the aggregation mechanism.A significant decrease of the amount, , of adsorbed polymer is observed with non-equilibrium bridging. When both mechanisms simultaneously contribute to the aggregation, the value of depends on their relative importance. In the intermediate range of copolymer dose their respective contributions are critically sensitive to the details of the mixing step and stirring, leading to non reproducible experimental results. 相似文献
103.
M~++BrCN─→MCN~++Br气相反应的从头算研究朱荣顺,戴树珊(云南大学化学系,昆明,650091)关键词气相反应,过渡金属阳离子,溴化氰,从头算,相对论赝势对过渡金属离子与一些小分子的气相反应已有大量的实验和理论研究[1~5],MichelS... 相似文献
104.
V. A. Livshits B. G. Dzikovskii V. P. Tsybyshev B. B. Meshkov 《Russian Chemical Bulletin》1996,45(7):1563-1571
Isotherms of the binding of dodecyl sulfate anions (DDS–)and Na+ counterions during their coadsorption with a nonionic polymer. proxanol (PR). at the interface of dodecane-water emulsions have been measured by conductometry and Na-selective potentiometry. The adsorption of DDS– and PR is concurrent. The affinity constant of PR to the interface determined by the Langmuir model decreases as the concentration of PR increases, and the surface concentration of DDS– tends to a nonzero limiting value at high concentrations of PR. The surface (o) and electrokinetic () potentials at the interface have been determined at various polymer concentrations by the spin probe and electrophoresis methods. The average dielectric permeability and density of polymer segments in We adsorption layer have been determined by ESR. The lower boundary of the hydrodynamic thickness of the polymer adsorption layer at the interface has been estimated from the dependences of o and on the ionic strength.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1653–1661, July, 1996. 相似文献
105.
Rabindra N. Roy Lakshmi N. Roy Jason G. Grant Mason P. Cummins Bennett J. Tabor III Sarah J. Richards Curtis A. Himes Bret R. Lively Penny L. Blackwell Ashley N. Simon 《Journal of solution chemistry》2002,31(11):861-872
The values of the second dissociation constant, pK
2, for the dissociation of the NH+ charge center of the zwitterionic buffer compounds 4-(N-morpholino)butanesulfonic acid (MOBS), and N-(2-hydroxyethyl)piperazine-N-4-butanesulfonic acid (HEPBS) have been determined from 5 to 55°C, including, 37°C at intervals of 5°C. The electromotive-force (emf) measurements have been made utilizing hydrogen electrodes and silver–silver chloride electrodes. The value of pK
2 for MOBS was found to be 7.702 ± 0.0005, and 8.284 ± 0.0004 for HEPBS, at 25°C, respectively. The related thermodynamic quantities, G
o, H
o, S
o, and C
p
o for the dissociation processes of MOBS and HEPBS have been derived from the temperature coefficients of pK
2. Both the MOBS and HEPBS buffer materials are useful as primary pH standards for the control of pH 7.3 to 8.6 in the region close to that of physiological fluids. 相似文献
106.
107.
We consider an Ising model with Kac potential dK(¦x¦) which may have arbitrary sign, and show, following Gates and Penrose, that the free energy in the classical limit0+ can be obtained from a variational principle. When the Fourier transform of the potential has its maximum atp=0 one recovers the usual mean-field theory of magnetism. When the maximum occurs forp
00, however, one obtains an oscillatory or helicoidal phase in which the magnetization near the critical point oscillates with period 2/¦p
0¦. An example with a potential possessing parameter-dependent oscillations is shown to exhibit crossover phenomena and a multicritical Lifshitz point in the classical limit. 相似文献
108.
H. R. Jauslin 《Journal of statistical physics》1986,42(3-4):573-585
The stationary probability density of Fokker-Planck models with weak noise is asymptotically of the form exp[–1 /(q)]. If is smooth, it satisfies a Hamilton-Jacobi equation at zero energy and can be interpreted as the action of an associated Hamiltonian system. Under this assumption, has the properties of a Liapounov function, and can be used, e.g., as a thermodynamic potential in nonequilibrium steady states. We consider systems having several attractors and show, by applying Melnikov's method to the associated Hamiltonian, that in general is not differentiable. A small perturbation of a model with differentiable leads to a nondifferentiable . The method is illustrated on a model used in the treatment of the unstable mode in a laser. 相似文献
109.
A new scheme has been developed for determining the parameters of the local one-electron potential in molecules and solids. The scheme is based on interpretation of the experimental X-ray absorption near edge struucture. The scheme is an extension of the method for solving the inverse problem of XANES theory suggested by one of the authors. In this scheme, oscillator strengths and maximum heights are considered along with the energy and half-width of spectral maxima. The scheme is used for determining the intraatomic potential in the nitrogen molecule.Original Russian Text Copyright © 2004 by Yu. F. Migal and O. M. Kholodova__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 6, pp. 986–989, November–December, 2004. 相似文献
110.
Xiu Hui Lu Hai Bin Yu Wei Rong Wu Yue Hua Xu 《International journal of quantum chemistry》2007,107(2):451-457
Mechanisms of the cycloaddition reaction between singlet difluoromethylene carbene and acetone have been investigated with the second‐order Møller–Plesset (MP2)/6‐31G* method, including geometry optimization and vibrational analysis. Energies for the involved stationary points on the potential energy surface (PES) are corrected by zero‐point energy (ZPE) and CCSD(T)/6‐31G* single‐point calculations. From the PES obtained with the CCSD(T)//MP2/6‐31G* method for the cycloaddition reaction between singlet difluoromethylene carbene and acetone, it can be predicted that path B of reactions 2 and 3 should be two competitive leading channels of the cycloaddition reaction between difluoromethylene carbene and acetone. The former consists of two steps: (i) the two reactants first form a four‐membered ring intermediate, INT2, which is a barrier‐free exothermic reaction of 97.8 kJ/mol; (ii) the intermediate INT2 isomerizes to a four‐membered product P2b via a transition state TS2b with an energy barrier of 24.9 kJ/mol, which results from the methyl group transfer. The latter proceeds in three steps: (i) the two reactants first form an intermediate, INT1c, through a barrier‐free exothermic reaction of 199.4 kJ/mol; (ii) the intermediate INT1c further reacts with acetone to form a polycyclic intermediate, INT3, which is also a barrier‐free exothermic reaction of 27.4 kJ/mol; and (iii) INT3 isomerizes to a polycyclic product P3 via a transition state TS3 with an energy barrier of 25.8 kJ/mol. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献