全文获取类型
收费全文 | 7905篇 |
免费 | 1205篇 |
国内免费 | 1020篇 |
专业分类
化学 | 5693篇 |
晶体学 | 47篇 |
力学 | 515篇 |
综合类 | 69篇 |
数学 | 942篇 |
物理学 | 2864篇 |
出版年
2024年 | 21篇 |
2023年 | 138篇 |
2022年 | 253篇 |
2021年 | 289篇 |
2020年 | 318篇 |
2019年 | 302篇 |
2018年 | 224篇 |
2017年 | 207篇 |
2016年 | 323篇 |
2015年 | 371篇 |
2014年 | 384篇 |
2013年 | 528篇 |
2012年 | 619篇 |
2011年 | 719篇 |
2010年 | 458篇 |
2009年 | 452篇 |
2008年 | 513篇 |
2007年 | 447篇 |
2006年 | 439篇 |
2005年 | 417篇 |
2004年 | 291篇 |
2003年 | 256篇 |
2002年 | 262篇 |
2001年 | 227篇 |
2000年 | 177篇 |
1999年 | 171篇 |
1998年 | 165篇 |
1997年 | 141篇 |
1996年 | 152篇 |
1995年 | 160篇 |
1994年 | 124篇 |
1993年 | 107篇 |
1992年 | 77篇 |
1991年 | 104篇 |
1990年 | 62篇 |
1989年 | 61篇 |
1988年 | 49篇 |
1987年 | 34篇 |
1986年 | 22篇 |
1985年 | 18篇 |
1984年 | 12篇 |
1983年 | 11篇 |
1982年 | 13篇 |
1981年 | 5篇 |
1980年 | 1篇 |
1979年 | 2篇 |
1976年 | 1篇 |
1966年 | 1篇 |
1957年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
171.
Although the theories and potential applications of intermolecular multiple-quantum coherences (iMQCs) have been under active investigations for over a decade, discussion of iMQC NMR signal formation was mainly confined in the time domain. In this paper, a full line-shape theory was developed to describe iMQC signals in the frequency domain. Relevant features of the line shape, such as peak height, linewidth, and phase, were investigated in detail. Predictions based on the theory agree well with experimental and simulated results. Since radiation-damping effects always couple with iMQCs in highly polarized liquid-state NMR systems, and strongly radiation-damped signals have many spectral characteristics similar to those of iMQCs, a detailed comparison was also made between them from different spectral aspects. With detailed comparison of peak height, linewidth, and phase, this work demonstrates that the iMQC and radiation-damping phenomena result from two completely different physical mechanisms despite that both present similar signal features and coexist in highly polarized liquid-state NMR systems. 相似文献
172.
The electrochemical carbon dioxide reduction reaction (CO2RR) offers a promising solution to mitigate carbon emission and at the same time generate valuable carbonaceous chemicals/fuels. Single atom catalysts (SACs) are encouraging to catalyze the electrochemical CO2RR due to the tunable electronic structure of the central metal atoms, which can regulate the adsorption energy of reactants and reaction intermediates. Moreover, SACs form a bridge between homogeneous and heterogeneous catalysts, providing an ideal platform to explore the reaction mechanism of electrochemical reactions. In this review, we first discuss the strategies for promoting the CO2RR performance, including suppression of the hydrogen evolution reaction (HER), generation of C1 products and formation of C2+ products. Then, we summarize the recent developments in regulating the structure of SACs toward the CO2RR based on the above aspects. Finally, several issues regarding the development of SACs for the CO2RR are raised and possible solutions are provided.The electrochemical carbon dioxide reduction reaction (CO2RR) offers a promising solution to mitigate carbon emission and at the same time generate valuable carbonaceous chemicals/fuels. 相似文献
173.
174.
175.
Yongjin Xu Beisheng Kang Xuetai Chen Yuanba Cai Yonghan Hu Jiaxi Lu 《Journal of Cluster Science》1992,3(2):167-177
Complex Co4mp4(Hmp)(PBu
3
n
)3 (1) (H2mp=o-Mercaptophenol) was obtained from the reaction of CoCl2 and H2mp in the presence of PBu
n
3 and NaOMe with restricted oxidation. X-ray crystallographic data: triclinic, space group
,a=15.657(5) Å,b=20.469(8) Å,c=12.383(3) Å,=93.59(3)°, =112.45(2)°, =93.65(3)°,V=3648.7 Å3,Z=2,D
c
=1.33 g/cm3;R=0.065. The molecule consists of four cobalt atoms unsymmetrically bridged by S or S and O atoms from four of the five mp ligands. The fifth mp is terminally chelated to Co(4) which is in a distorted trigonal bipyramidal geometry, while Co(1)-Co(3) are square pyramidal. Atom Co(2) is bonded to Co(1) and Co(3) (average distance 2.632 Å) with strong interactions while Co(4) is only loosely connected to Co(1) (3.402 Å) and Co(3) (2.956 Å) through oxygen bridges and a hydrogen bond. The different coordination environments O2S2P, S4P, and O4S of the cobalt atoms make the molecule highly asymmetrical. XPS fitting data confirm the difference of the Co atoms. FABMS data indicate the possible fragmentation routes. The complex is paramagnetic with eff=5.2 B. 相似文献
176.
Summary We provide a convergence rate analysis for a variant of the domain decomposition method introduced by Gropp and Keyes for solving the algebraic equations that arise from finite element discretization of nonsymmetric and indefinite elliptic problems with Dirichlet boundary conditions in 2. We show that the convergence rate of the preconditioned GMRES method is nearly optimal in the sense that the rate of convergence depends only logarithmically on the mesh size and the number of substructures, if the global coarse mesh is fine enough.This author was supported by the National Science Foundation under contract numbers DCR-8521451 and ECS-8957475, by the IBM Corporation, and by the 3M Company, while in residence at Yale UniversityThis author was supported by the Applied Mathematical Sciences subprogram of the Office of Energy Research, U.S. Department of Energy under Contract W-31-109-Eng-38This author was supported by the National Science Foundation under contract number ECS-8957475, by the IBM Corporation, and by the 3M Company 相似文献
177.
178.
179.
Wu G Cai ZW Bednarz MS Kocy OR Gavai AV Godfrey JD Washburn WN Poss MA Sher PM 《Journal of combinatorial chemistry》2005,7(1):99-108
Benzylic and allylic organozinc and Grignard reagents have been added to resin-bound imines to provide alpha-branched secondary amines. Many functional groups, including electrophilic groups, were compatible with this methodology. Three modules--a resin-bound primary amine, an aromatic aldehyde, and the organometallic--were independently varied to produce a combinatorial library of alpha-branched secondary amines designed as beta-3 adrenergic receptor agonists. 相似文献
180.
Liu L Cai X Li Y Richards O'Grady E Farrar JM 《The Journal of chemical physics》2004,121(8):3495-3506
The charge transfer and deuterium ion transfer reactions between D(2)O(+) and C(2)H(4) have been studied using the crossed beam technique at relative collision energies below one electron volt and by density functional theory (DFT) calculations. Both direct and rearrangement charge transfer processes are observed, forming C(2)H(4) (+) and C(2)H(3)D(+), respectively. Independent of collision energy, deuterium ion transfer accounts for approximately 20% of the reactive collisions. Between 22 and 36 % of charge transfer collisions occur with rearrangement. In both charge transfer processes, comparison of the internal energy distributions of products with the photoelectron spectrum of C(2)H(4) shows that Franck-Condon factors determine energy disposal in these channels. DFT calculations provide evidence for transient intermediates that undergo H/D migration with rearrangement, but with minimal modification of the product energy distributions determined by long range electron transfer. The cross section for charge transfer with rearrangement is approximately 10(3) larger than predicted from the Rice-Ramsperger-Kassel-Marcus isomerization rate in transient complexes, suggesting a nonstatistical mechanism for H/D exchange. DFT calculations suggest that reactive trajectories for deuterium ion transfer follow a pathway in which a deuterium atom from D(2)O(+) approaches the pi-cloud of ethylene along the perpendicular bisector of the C-C bond. The product kinetic energy distributions exhibit structure consistent with vibrational motion of the D-atom in the bridged C(2)H(4)D(+) product perpendicular to the C-C bond. The reaction quantitatively transforms the reaction exothermicity into internal excitation of the products, consistent with mixed energy release in which the deuterium ion is transferred in a configuration in which both the breaking and the forming bonds are extended. 相似文献