全文获取类型
收费全文 | 13499篇 |
免费 | 1612篇 |
国内免费 | 1350篇 |
专业分类
化学 | 3462篇 |
晶体学 | 204篇 |
力学 | 1565篇 |
综合类 | 299篇 |
数学 | 6941篇 |
物理学 | 3990篇 |
出版年
2024年 | 17篇 |
2023年 | 119篇 |
2022年 | 220篇 |
2021年 | 300篇 |
2020年 | 375篇 |
2019年 | 360篇 |
2018年 | 359篇 |
2017年 | 479篇 |
2016年 | 515篇 |
2015年 | 421篇 |
2014年 | 694篇 |
2013年 | 1150篇 |
2012年 | 684篇 |
2011年 | 830篇 |
2010年 | 682篇 |
2009年 | 838篇 |
2008年 | 874篇 |
2007年 | 848篇 |
2006年 | 779篇 |
2005年 | 701篇 |
2004年 | 567篇 |
2003年 | 567篇 |
2002年 | 548篇 |
2001年 | 489篇 |
2000年 | 476篇 |
1999年 | 407篇 |
1998年 | 347篇 |
1997年 | 327篇 |
1996年 | 248篇 |
1995年 | 211篇 |
1994年 | 142篇 |
1993年 | 119篇 |
1992年 | 93篇 |
1991年 | 86篇 |
1990年 | 72篇 |
1989年 | 70篇 |
1988年 | 64篇 |
1987年 | 44篇 |
1986年 | 33篇 |
1985年 | 59篇 |
1984年 | 60篇 |
1983年 | 20篇 |
1982年 | 40篇 |
1981年 | 29篇 |
1980年 | 16篇 |
1979年 | 28篇 |
1978年 | 15篇 |
1977年 | 6篇 |
1976年 | 8篇 |
1975年 | 5篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
1.
2.
本文首先对双层规划的一个特殊例子即道德风险模型中使用的一阶条件方法(FOA)做简要的梳理,然后提出一种更为一般的使FOA有效的原则与方法。新方法主要依赖于代理人对委托人设置的目标的最优反应映射是否存在不动点,这个性质不要求原问题与用一阶条件放松以后的问题之间的约束集等价,从而也不要求代理人的期望效用对行动具有全局凹性。在新方法下,可以用较为简单的方法证明FOA在以下两种情形之一有效,即如果分布函数是概率分布的凸组合或者分布函数来自某些特殊的指数族分布。 相似文献
3.
Chemical bonding in representative astrophysically relevant neutral,cation, and anion HCnH chains 下载免费PDF全文
Ioan Baldea 《中国物理 B》2022,31(12):123101-123101
Most existing studies assign a polyynic and cumulenic character of chemical bonding in carbon-based chains relying on values of the bond lengths. Building on our recent work, in this paper we add further evidence on the limitations of such an analysis and demonstrate the significant insight gained via natural bond analysis. Presently reported results include atomic charges, natural bond order and valence indices obtained from ab initio computations for representative members of the astrophysically relevant neutral and charged HC2k/2k+1H chain family. They unravel a series of counter-intuitive aspects and/or help naive intuition in properly understanding microscopic processes, e.g., electron removal from or electron attachment to a neutral chain. Demonstrating that the Wiberg indices adequately quantify the chemical bonding structure of the HC2k/2k+1H chains—while the often heavily advertised Mayer indices do not—represents an important message conveyed by the present study. 相似文献
4.
5.
Nitin P. Lobo K.V. Ramanathan T. Narasimhaswamy 《Magnetic resonance in chemistry : MRC》2020,58(11):988-1009
In this review, methods to obtain the orientational order of topologically variant molecular mesogens using by one- and two-dimensional (2D) solid-state 13C nuclear magnetic resonance (NMR) spectroscopy are described. Besides 13C chemical shifts, the 13C─1H dipolar couplings measured from 2D-separated local field (SLF) technique are used for computing the order parameters of a variety of mesogens. The investigated molecules are composed of a variable number of rings in the core, that is, core ranging from simply one ring to five rings. Among the mesogens investigated, a special focus has been placed on mesogens with thiophene rings, which are gaining popularity as liquid crystalline organic semiconductors. The replacement of a phenyl ring by thiophene in the core has a dramatic influence on molecular topology, as observed from the measured order parameters. The review highlights the advantages of the 2D SLF method for understanding the local dynamics and for mapping the topology of mesogens through the measured order parameters. SLF NMR studies of as many as 24 molecular mesogens that vary in terms of the molecular structure as well as topology are covered in the review. Order parameters of the rings have been estimated from the 13C─1H dipolar couplings in the nematic, smectic A, smectic C, and tilted hexatic phases as well as in B1 and B2 mesophases of various mesogens. It is anticipated that, in the years to come, the 2D SLF method would provide advanced molecular information on structurally complex mesogens that are emerging in liquid crystal science through the incessant efforts of synthetic chemists. The mini review covers the orientational order of topologically variant molecular mesogens determined by 1D and 2D solid-state 13C NMR spectroscopy. Accordingly, rod-like, bent-core, and thiophene mesogens were subjected to 2D SLF measurements to get the order parameters from which the topology was established. The replacement of phenyl ring by thiophene and its influence on order parameters as well as on molecular topology is also discussed. 相似文献
6.
Benni Du 《Molecular physics》2020,118(2)
Kinetics and mechanism of the gas-phase reaction of CH3C(O)OCH(CH3)CH2OCH3 (MPA) with OH radicals in the presence of O2 and NO have been investigated theoretically by performing a high and reliable level of theory, viz., CCSD(T)/6-311?+?G(d,p)//BH&HLYP/6-311++G(d,p)?+?0.9335×ZPE. The calculations predict that the H-abstraction from the ?CH2?O? position of MPA is the most facile channel, which leads to the formation of the corresponding alkoxy radicals CH3C(O)OCH(CH3)C(O ?)HOCH3 under atmospheric conditions. This activated radicals CH3C(O)OCH(CH3)C(O ?)HOCH3 will undergo further rearrangement, fragmentation and oxidative reactions and predominantly leads to the formation of various products (methyl formate HC(O)OCH3 and acetic anhydride CH3C(O)OC(O)CH3). In the presence of water, acetic anhydride can convert into acetic acid CH3C(O)OH via the hydrolysis reaction. The calculated total rate constants over the temperature range 263–372?K are used to derive a negative activation energy (Ea= ?5.88 kJ/mol) and an pre-exponential factor (A?=?1.78×10?12 cm3 molecule?1 s?1). The obtained Arrhenius parameters presented here are in strong agreement with the experimental values. Moreover, the temperature dependence of the total rate constant over a temperature range of 263?1000?K can be described by k?=?5.60 × 10?14×(T/298?K)3.4×exp(1725.7?K/T) cm3 molecule?1 s?1. 相似文献
7.
Yingchun Wu Haipeng Li Xuecheng Wu Gérard Gréhan Lutz Mädler Cyril Crua 《Proceedings of the Combustion Institute》2019,37(3):3211-3218
Droplet evaporation characterization, although of great significance, is still challenging. The recently developed phase rainbow refractometry (PRR) is proposed as an approach to measuring the droplet temperature, size as well as evaporation rate simultaneously, and is applied to a single flowing n-heptane droplet produced by a droplet-on-demand generator. The changes of droplet temperature and evaporation rate after a transient spark heating are reflected in the time-resolved PRR image. Results show that droplet evaporation rate increases with temperature, from ?1.28 m2/s at atmospheric 293 K to a range of (?1.5, ?8) m2/s when heated to (294, 315) K, agreeing well with the Maxwell and Stefan–Fuchs model predictions. Uncertainty analysis suggests that the main source is the indeterminate gradient inside droplet, resulting in an underestimation of droplet temperature and evaporation rate. With the demonstration on simultaneous measurements of droplet refractive index as well as droplet transient and local evaporation rate in this work, PRR is a promising tool to investigate single droplet evaporation in real engine conditions. 相似文献
8.
《Physics letters. A》2019,383(17):2090-2092
In this paper, we have used Monte Carlo (MC) method to simulate and study the temperature and doping effects on the electric conductivity of fullerene (C60). The results show that the band gap has reduced by the doping and the charge carrier transport is facilitated from valence band to conduction band by the temperature where is touched a 300 K. In this case, the conductivity reached a value of . The electric conductivity of C60 can increase by the triphenylmethane dye crystal violet (CV) alkali metal to reach at 303 K. Our results of MC simulation have a good agreement with those extracted from literature [10], [33]. 相似文献
9.
10.
Lin Surong 《Annals of Differential Equations》2006,22(4):517-523
The singularly perturbed boundary value problem for nonlinear higher order ordinary differential equation involving two small parameters has been considered. Under appropriate assumptions, for the three cases:ε/μ2→0(μ→0),μ2/ε→0 (ε→0) andε=μ2, the uniformly valid asymptotic solution is obtained by using the expansion method of two small parameters and the theory of differential inequality. 相似文献