全文获取类型
收费全文 | 11144篇 |
免费 | 1554篇 |
国内免费 | 1624篇 |
专业分类
化学 | 10828篇 |
晶体学 | 343篇 |
力学 | 112篇 |
综合类 | 73篇 |
数学 | 567篇 |
物理学 | 2399篇 |
出版年
2024年 | 40篇 |
2023年 | 163篇 |
2022年 | 407篇 |
2021年 | 466篇 |
2020年 | 613篇 |
2019年 | 450篇 |
2018年 | 407篇 |
2017年 | 386篇 |
2016年 | 576篇 |
2015年 | 594篇 |
2014年 | 644篇 |
2013年 | 1092篇 |
2012年 | 638篇 |
2011年 | 612篇 |
2010年 | 550篇 |
2009年 | 646篇 |
2008年 | 670篇 |
2007年 | 772篇 |
2006年 | 660篇 |
2005年 | 614篇 |
2004年 | 527篇 |
2003年 | 459篇 |
2002年 | 314篇 |
2001年 | 251篇 |
2000年 | 280篇 |
1999年 | 197篇 |
1998年 | 193篇 |
1997年 | 175篇 |
1996年 | 174篇 |
1995年 | 148篇 |
1994年 | 91篇 |
1993年 | 80篇 |
1992年 | 66篇 |
1991年 | 39篇 |
1990年 | 35篇 |
1989年 | 30篇 |
1988年 | 41篇 |
1987年 | 31篇 |
1986年 | 29篇 |
1985年 | 35篇 |
1984年 | 20篇 |
1983年 | 9篇 |
1982年 | 17篇 |
1981年 | 9篇 |
1980年 | 11篇 |
1979年 | 9篇 |
1977年 | 7篇 |
1976年 | 7篇 |
1975年 | 8篇 |
1973年 | 12篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
41.
An FT-IR study of pyrrole self-association in CCl4 solutions was carried out. According to the IR measurements, pyrrole forms self-associated dimeric species via N-H?π hydrogen bonding. This was also confirmed by quantum chemical calculations for pyrrole monomer and dimer at B3LYP/6-31++G(d,p) level of theory. A T-shaped minimum was located on B3LYP/6-31++G(d,p) PES of pyrrole dimer characterized with a hydrogen bond of an N-H?π type, with centers-of-mass separation of monomeric units of 4.520 Å, H?π distance of 2.475 Å, the interplanar angle between the two monomeric units being 72.9°. The anharmonic vibrational frequency shift upon dimer formation calculated on the basis of 1D DFT vibrational potentials is in excellent agreement with the experimental data (84 vs. 87 cm−1). Harmonic vibrational analysis predicts somewhat smaller shift (68 cm−1). On the basis of NIR spectroscopic data, anharmonicity constants for the 2ν(N-H) and 2ν(N-H?π) vibrational transitions were calculated. The orientational dynamics of monomeric and self-associated pyrrole species was studied within the framework of the transition dipole moment time correlation function formalism. The period of essentially free rotation in the condensed phase reduces from 0.05 ps for the monomeric pyrrole to 0.02 ps for the proton-donor molecule within the dimer. 相似文献
42.
43.
This paper deals with the optimal control of a one-machine two-product manufacturing system with setup changes, operating in a continuous time dynamic environment. The system is deterministic. When production is switched from one product to the other, a known constant setup time and a setup cost are incurred. Each product has specified constant processing time and constant demand rate, as well as an infinite supply of raw material. The problem is formulated as a feedback control problem. The objective is to minimize the total backlog, inventory and setup costs incurred over a finite horizon. The optimal solution provides the optimal production rate and setup switching epochs as a function of the state of the system (backlog and inventory levels). For the steady state, the optimal cyclic schedule is determined. To solve the transient case, the system's state space is partitioned into mutually exclusive regions such that with each region, the optimal control policy is determined analytically. 相似文献
44.
析氢反应动力学的交流阻抗法研究 总被引:1,自引:0,他引:1
利用交流阻抗法测定析氢电化学动力学参数,得到与极化曲线法一致的结果,为确定复杂析氢过程速率的决定步骤提供了判据。 相似文献
45.
We address in this paper the problem of finding an optimal strategy for dealing with bottleneck machines and bottleneck parts in the cell formation process in group technology. Three types of economic decisions are considered: subcontracting, machine duplication and intercell moves. The problem is formulated as a minimum weighted node covering problem in a hypergraph, and we show that it can be solved in polynomial time by finding a maximum weighted stable set in a bipartite graph. We extend this result to cellular manufacturing systems in which the sequence of operations of each part is known in advance. 相似文献
46.
W. Brüggemann K. Fischer H. Jahnke 《Journal of Mathematical Modelling and Algorithms》2003,2(2):153-169
In Part I of this study, we suggest to identify an operations research (OR) problem with the equivalence class of models describing the problem and enhance the standard computer-science theory of computational complexity to be applicable to this situation of an often model-based OR context. The Discrete Lot-sizing and Scheduling Problem (DLSP) is analysed here in detail to demonstrate the difficulties which can arise if these aspects are neglected and to illustrate the new theoretical concept. In addition, a new minimal model is introduced for the DLSP which makes this problem eventually amenable to a rigorous analysis of its computational complexity. 相似文献
47.
Tatiana B. Mikenas Vladimir A. Zakharov Lyudmila G. Echevskaya Mikhail A. Matsko 《Journal of polymer science. Part A, Polymer chemistry》2007,45(22):5057-5066
The effects of polymerization temperature, polymerization time, ethylene and hydrogen concentration, and effect of comonomers (hexene‐1, propylene) on the activity of supported catalyst of composition LFeCl2/MgCl2‐Al(i‐Bu)3 (L = 2,6‐bis[1‐(2,6‐dimethylphenylimino)ethyl] pyridyl) and polymer characteristics (molecular weight (MW), molecular‐weight distribution (MWD), molecular structure) have been studied. Effective activation energy of ethylene polymerization over LFeCl2/MgCl2‐Al(i‐Bu)3 has a value typical of supported Ziegler–Natta catalysts (11.9 kcal/mol). The polymerization reaction is of the first order with respect to monomer at the ethylene concentration >0.2 mol/L. Addition of small amounts of hydrogen (9–17%) significantly increases the activity; however, further increase in hydrogen concentration decreases the activity. The IRS and DSC analysis of PE indicates that catalyst LFeCl2/MgCl2‐Al(i‐Bu)3 has a very low copolymerizing ability toward propylene and hexene‐1. MW and MWD of PE produced over these catalysts depend on the polymerization time, ethylene and hexene‐1 concentration. The activation effect of hydrogen and other kinetic features of ethylene polymerization over supported catalysts based on the Fe (II) complexes are discussed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5057–5066, 2007 相似文献
48.
49.
The trisilanol 1,3,5‐(HOi‐Bu2Si)3C6H3 ( 7 ), prepared in three steps from 1,3,5‐tribromobenzene via the intermediates 1,3,5‐(Hi‐Bu2Si)3C6H3 ( 8 ) and 1,3,5‐(Cli‐Bu2Si)3C6H3 ( 9 ) forms an equimolar complex with trans‐bis(4‐pyridyl)ethylene (bpe), 7 ·bpe, whose structure was investigated by X‐ray crystallography. The hydrogen‐bonded network features a number of SiO? H(H)Si and SiO? H hydrogen bridges. Evidence was found for cooperative strengthening within the sequential hydrogen bonds. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
50.
Praveen K. Tandon Gayatri Sumita Sahgal Manish Srivastava Santosh B. Singh 《应用有机金属化学》2007,21(3):135-138
Catalytic activities of three transition metals, as iridium (III) chloride, rhodium (III) chloride and palladium (II) chloride, were compared in the oxidation of six aromatic aldehydes (benzaldehyde, p‐chloro benzaldehyde, p‐nitro benzaldehyde, m‐nitro benzaldehyde, p‐methoxy benzaldehyde and cinnamaldehyde), two hydrocarbons (viz. (anthracene and phenanthrene)) and one aromatic and one cyclic alcohol (cyclohexanol and benzyl alcohol) by 50% H2O2. The presence of traces (substrate: catalyst ratio equal to 1:62500 to 1:1961) of the chlorides of iridium(III), rhodium(III) and palladium(II) catalyze these oxidations, resulting in good to excellent yields. It was observed that in most of the cases palladium(II) chloride is the most efficient catalyst. Conditions for the highest and most economical yields were obtained. Deviation from the optimum conditions decreases the yields. Oxidation in aromatic aldehydes is selective at the aldehydeic group only and other groups remain unaffected. This new, simple and economical method, which is environmentally safe, also requires less time. Reactive species of catalysts, existing in the reaction mixture are also discussed. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献