全文获取类型
收费全文 | 3864篇 |
免费 | 844篇 |
国内免费 | 501篇 |
专业分类
化学 | 1509篇 |
晶体学 | 59篇 |
力学 | 196篇 |
综合类 | 58篇 |
数学 | 910篇 |
物理学 | 2477篇 |
出版年
2024年 | 7篇 |
2023年 | 56篇 |
2022年 | 148篇 |
2021年 | 138篇 |
2020年 | 134篇 |
2019年 | 112篇 |
2018年 | 116篇 |
2017年 | 186篇 |
2016年 | 189篇 |
2015年 | 160篇 |
2014年 | 303篇 |
2013年 | 317篇 |
2012年 | 264篇 |
2011年 | 306篇 |
2010年 | 228篇 |
2009年 | 270篇 |
2008年 | 272篇 |
2007年 | 231篇 |
2006年 | 197篇 |
2005年 | 203篇 |
2004年 | 173篇 |
2003年 | 148篇 |
2002年 | 128篇 |
2001年 | 107篇 |
2000年 | 98篇 |
1999年 | 100篇 |
1998年 | 82篇 |
1997年 | 63篇 |
1996年 | 75篇 |
1995年 | 74篇 |
1994年 | 46篇 |
1993年 | 33篇 |
1992年 | 28篇 |
1991年 | 27篇 |
1990年 | 25篇 |
1989年 | 27篇 |
1988年 | 20篇 |
1987年 | 15篇 |
1986年 | 10篇 |
1985年 | 11篇 |
1984年 | 16篇 |
1983年 | 7篇 |
1982年 | 10篇 |
1981年 | 15篇 |
1980年 | 7篇 |
1979年 | 7篇 |
1978年 | 7篇 |
1977年 | 5篇 |
1974年 | 2篇 |
1973年 | 3篇 |
排序方式: 共有5209条查询结果,搜索用时 30 毫秒
91.
92.
A Rhine river sediment sample was spiked with tributyltin (TBT), equilibrated for ten days and the tributyltin extraction efficiency was optimised using a simplex algorithm. Analysis was effected using hydride generation gas chromatography-atomic absorption spectroscopy (GC-AAS) apparatus. The results show that, in this sediment sample, different molarities of HCl in methanol extract different species with varying extraction efficiencies. The least polar extraction solution extracted TBT more efficiently, whilst DBT and MBT require molar solution of HCl in methanol for efficient extraction. 相似文献
93.
Eric D BalighianJoel F Liebman 《Journal of fluorine chemistry》2002,116(1):35-39
It is well established that atomic fluorine has a miserly high ionization energy and avariciously high electron affinity. Yet, as was shown some 30 years ago, the latter value is anomalously low-linear extrapolation shows the value to be some 110 kJ/mol less than expected by comparison to the heavier halogens. Related literature investigation extended this anomaly to nitrogen and oxygen and their (valence) isoelectronic congeners. We extend it to related cationic species and thereby the noble gases and alkali metals, and the aforementioned species are better understood. We thus ask if the ionization energy/electron affinity anomaly of fluorine remains an anomaly. 相似文献
94.
Separation of polar and non-polar analytes using dimethyl sulfoxide-modified subcritical water 总被引:1,自引:0,他引:1
Separations using methanol–water or acetonitrile–water mixtures at different temperatures have been well investigated in reversed-phase liquid chromatography. However, reversed-phase separation with dimethyl sulfoxide (DMSO)–water mixtures is much less studied. In this work, separations of polyhydroxybenzenes, phenol derivatives, benzene, toluene, ethylbenzene, and xylenes (BTEX), and polycyclic aromatic hydrocarbons (PAHs) with DMSO-modified subcritical water were performed at several temperatures to evaluate the effect of temperature on the elution strength of DMSO–water mixtures. The column efficiency obtained by using DMSO-modified subcritical water was also studied. Finally, the resolution of ethylbenzene and p-xylene was investigated. 相似文献
95.
Organic nanocrystals of 1,3,5-triphenyl-2-pyrazoline(TPP) with a series of sizes were synthesized by reprecipitation method.The luminescence quantum efficiency of TPP nanocrystals increases from 24.2% for the nanocrystals with an average size of 300nm to 34.6% for those with an average size of 20nm.Surface capping by polyvinyl pyrrolidone(PVP) will improve the quantum efficiency of TPP nanocrystals.The size-dependence and capping-induced variation of the luminescence quantum efficiency was elucidated in viewpoint of aggregation quenching and the equilibrium between the TPP monomers and the aggregates in TPP nanocrystals. 相似文献
96.
有机硅化合物是半导体工业中产生硅元件的基本原料和有机合成中的重要试剂,是多年来大家研究较多的分子体系之一.本文报导了用同步辐射加速器产生的真空紫外光,电离St(CH3hCI。分子.在50-120n-m波长范围内,测量了各种离子产物与真空紫外光波长的关系,推算得它的绝热电离电势和离子中几个化学键的键能.1实验装置和方法本工作在国家同步辐射实验室光化学实验站进行.进行分子真空紫外光电离研究的实验系统已在文献山中详细描述.同步辐射加速器产生的真空紫外光波长用Ne气的电离势标定,其误差<士0-Inln.单色仪的分辨率为河凸… 相似文献
97.
Samuel C. Perry Pui-ki Leung Ling Wang Carlos Ponce de León 《Current Opinion in Electrochemistry》2020
CO2 reduction processes continue to be developed for electrosynthesis, energy storage applications, and environmental remediation. A number of promising materials have shown high activity and selectivity to target reduction products. However, the progress has been mainly at a small laboratory scale, and the technical challenges of large scale CO2 reduction have not been considered adequately. This review covers recent advancements in catalyst materials and cell designs. The leading materials for CO2 reduction to a number of useful products are presented with their corresponding cell and reactor designs. The latest efforts to progress to industrially relevant scales are discussed, along with the challenges that must be met for carbon dioxide reduction to be a viable route for mass scale production. 相似文献
98.
The photoionization spectroscopy of Si(CH3)3Cl in the range of 50 -130 nm was studied with synchrotron radiation source. The adiabatic ionization potentials of molecule Si(CH3)3Cl and radical Si(CH3)3 are 10.06 ±0.02 eV and 7.00±0.03 eV respectively. In addition, the appearance potentials of Si(CH3)2Cl+, Si(CH3)3+, SiCl+ and SiCH3+ were determined:
AP(Si(CH3)2Cl+) =10.49±0.02eV, AP(Si(CH3)3+) = 11.91 ±0.02eV
AP(SiCl+) = 18.64 ±0.06eV, AP(SiCH3+)= 18.62 ±0.02eV
From these, some chemical bond energies of Si(CH3)3Cl+ were calculated:
D(Si(CH3)2Cl+ - CH3) =0.43 ±0.02eV, D(Si(CH3)3+ - Cl) = 1.85 ± 0.02eV
D(SiCH3+ - (2CH3 + Cl)) = 8.56 ± 0.06eV, D(SiCH3+ - 2CH3) =6.71±0.06eV
D(SiCl+ - 3CH3) = 8.58 ± 0.06eV, D(SiCl+- 2CH3) = 8.15 ±0.06eV
D(SiCH3+- (CH3 + Cl)) =8.13 ±0.06eV 相似文献
AP(Si(CH3)2Cl+) =10.49±0.02eV, AP(Si(CH3)3+) = 11.91 ±0.02eV
AP(SiCl+) = 18.64 ±0.06eV, AP(SiCH3+)= 18.62 ±0.02eV
From these, some chemical bond energies of Si(CH3)3Cl+ were calculated:
D(Si(CH3)2Cl+ - CH3) =0.43 ±0.02eV, D(Si(CH3)3+ - Cl) = 1.85 ± 0.02eV
D(SiCH3+ - (2CH3 + Cl)) = 8.56 ± 0.06eV, D(SiCH3+ - 2CH3) =6.71±0.06eV
D(SiCl+ - 3CH3) = 8.58 ± 0.06eV, D(SiCl+- 2CH3) = 8.15 ±0.06eV
D(SiCH3+- (CH3 + Cl)) =8.13 ±0.06eV 相似文献
99.
L. G. Chalmet R. L. Francis J. F. Lawrence 《Journal of Optimization Theory and Applications》1980,32(2):135-149
An example of design might be a warehouse floor (represented by a setS) of areaA, with unspecified shape. Givenm warehouse users, we suppose that useri has a known disutility functionf
isuch thatH
i(S), the integral off
iover the setS (for example, total travel distance), defines the disutility of the designS to useri. For the vectorH(S) with entriesH
i(S), we study the vector minimization problem over the set {H(S) :S a design} and call a design efficient if and only if it solves this problem. Assuming a mild regularity condition, we give necessary and sufficient conditions for a design to be efficient, as well as verifiable conditions for the regularity condition to hold. For the case wheref
iis thel
p-distance from warehouse docki, with 1<p<, a design is efficient if and only if it is essentially the same as a contour set of some Steiner-Weber functionf
=1
f
1++
m
f
m
,when the
i
are nonnegative constants, not all zero.This research was supported in part by the Interuniversity College for PhD Studies in Management Sciences (CIM), Brussels, Belgium; by the Army Research Office, Triangle Park, North Carolina; by a National Academy of Sciences-National Research Council Postdoctorate Associateship; and by the Operations Research Division, National Bureau of Standards, Washington, D.C. The authors would like to thank R. E. Wendell for calling Ref. 16 to their attention. 相似文献
100.
氟代乙烯阳离子的理论研究 总被引:1,自引:0,他引:1
用B3LYP和MP2方法及6-31G(d, p)、6-31+G(d, p)、6-311G(d, p)和6-311+G(d, p) 基组,对六种氟代乙烯阳离子做了理论研究,优化了它们的基电子态的结构,计算了对应分子的垂直电离势(VIP)和绝热电离势(AIP).结果表明,与具有非平面结构的乙烯阳离子不同,六种氟代乙烯阳离子都只具有平面结构;与分子结构相比,离子结构的C-C键增长, C-F键缩短, CCF键角变小. 自然布居分析计算表明,这些离子的正电荷主要分布在与F原子相连的C原子和各H原子上. B3LYP/6-311+G(d, p) 级别上计算的各分子的VIP和AIP值和实验值符合得很好. 使用含弥散基函数的基集可以明显提高这类分子的电离势的计算精度. 相似文献