全文获取类型
收费全文 | 2444篇 |
免费 | 631篇 |
国内免费 | 92篇 |
专业分类
化学 | 2587篇 |
晶体学 | 15篇 |
力学 | 148篇 |
综合类 | 3篇 |
数学 | 55篇 |
物理学 | 359篇 |
出版年
2024年 | 5篇 |
2023年 | 46篇 |
2022年 | 88篇 |
2021年 | 93篇 |
2020年 | 184篇 |
2019年 | 105篇 |
2018年 | 103篇 |
2017年 | 69篇 |
2016年 | 226篇 |
2015年 | 197篇 |
2014年 | 180篇 |
2013年 | 190篇 |
2012年 | 152篇 |
2011年 | 159篇 |
2010年 | 118篇 |
2009年 | 167篇 |
2008年 | 156篇 |
2007年 | 148篇 |
2006年 | 141篇 |
2005年 | 86篇 |
2004年 | 102篇 |
2003年 | 85篇 |
2002年 | 39篇 |
2001年 | 34篇 |
2000年 | 46篇 |
1999年 | 29篇 |
1998年 | 32篇 |
1997年 | 25篇 |
1996年 | 21篇 |
1995年 | 16篇 |
1994年 | 13篇 |
1993年 | 16篇 |
1992年 | 10篇 |
1991年 | 12篇 |
1990年 | 8篇 |
1989年 | 5篇 |
1988年 | 14篇 |
1987年 | 5篇 |
1985年 | 10篇 |
1984年 | 2篇 |
1982年 | 4篇 |
1981年 | 2篇 |
1978年 | 2篇 |
1976年 | 2篇 |
1975年 | 3篇 |
1974年 | 3篇 |
1973年 | 2篇 |
1969年 | 2篇 |
1968年 | 1篇 |
1967年 | 2篇 |
排序方式: 共有3167条查询结果,搜索用时 15 毫秒
71.
Andreas Uwe Meyer Karolína Straková Dr. Tomáš Slanina Prof. Dr. Burkhard König 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(25):8694-8699
Alkyl‐ and aryl vinyl sulfones were obtained by eosin Y (EY)‐mediated visible‐light photooxidation of sulfinate salts and the reaction of the resulting S‐centered radicals with alkenes. Optimized reaction conditions, the sulfinate and alkene scope, and X‐ray structural analyses of several reaction products are provided. A detailed spectroscopic study explains the reaction mechanism, which proceeds through the EY radical cation as key intermediate oxidizing the sulfinate salts. 相似文献
72.
Photoisomerization Mechanism of Ruthenium Sulfoxide Complexes: Role of the Metal‐Centered Excited State in the Bond Rupture and Bond Construction Processes 下载免费PDF全文
Dr. Huifang Li Lisheng Zhang lvyin Zheng Dr. Xun Li Dr. Xiaolin Fan Dr. Yi Zhao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(40):14285-14292
Phototriggered intramolecular isomerization in a series of ruthenium sulfoxide complexes, [Ru(L)(tpy)(DMSO)]n+ (where tpy=2,2’:6’,2’’‐terpyridine; DMSO=dimethyl sulfoxide; L=2,2’‐bipyridine (bpy), n=2; N,N,N’,N’‐tetramethylethylenediamine (tmen) n=2; picolinate (pic), n=1; acetylacetonate (acac), n=1; oxalate (ox), n=0; malonate (mal), n=0), was investigated theoretically. It is observed that the metal‐centered ligand field (3MC) state plays an important role in the excited state S→O isomerization of the coordinated DMSO ligand. If the population of 3MCS state is thermally accessible and no 3MCO can be populated from this state, photoisomerization will be turned off because the 3MCS excited state is expected to lead to fast radiationless decay back to the original 1GSS ground state or photodecomposition along the Ru2+?S stretching coordinate. On the contrary, if the population of 3MCS (or 3MCO) state is inaccessible, photoinduced S→O isomerization can proceed adiabatically on the potential energy surface of the metal‐to‐ligand charge transfer excited states (3MLCTS→3MLCTO). It is hoped that these results can provide valuable information for the excited state isomerization in photochromic d6 transition‐metal complexes, which is both experimentally and intellectually challenging as a field of study. 相似文献
73.
Dynamical Bifurcation in Gas‐Phase XH− + CH3Y SN2 Reactions: The Role of Energy Flow and Redistribution in Avoiding the Minimum Energy Path 下载免费PDF全文
Yaicel G. Proenza Prof. Miguel A. F. de Souza Prof. Ricardo L. Longo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(45):16220-16229
The gas‐phase reactions of XH? (X=O, S) + CH3Y (Y=F, Cl, Br) span nearly the whole range of SN2 pathways, and show an intrinsic reaction coordinate (IRC) (minimum energy path) with a deep well owing to the CH3XH???Y? (or CH3S????HF) hydrogen‐bonded postreaction complex. MP2 quasiclassical‐type direct dynamics starting at the [HX???CH3???Y]? transition‐state (TS) structure reveal distinct mechanistic behaviors. Trajectories that yield the separated CH3XH+Y? (or CH3S?+HF) products directly are non‐IRC, whereas those that sample the CH3XH???Y? (or CH3S????HF) complex are IRC. The IRCIRC/non‐IRC ratios of 90:10, 40:60, 25:75, 2:98, 0:100, and 0:100 are obtained for (X, Y)=(S, F), (O, F), (S, Cl), (S, Br), (O, Cl), and (O, Br), respectively. The properties of the energy profiles after the TS cannot provide a rationalization of these results. Analysis of the energy flow in dynamics shows that the trajectories cross a dynamical bifurcation, and that the inability to follow the minimum energy path arises from long vibration periods of the X?C???Y bending mode. The partition of the available energy to the products into vibrational, rotational, and translational energies reveals that if the vibrational contribution is more than 80 %, non‐IRC behavior dominates, unless the relative fraction of the rotational and translational components is similar, in which case a richer dynamical mechanism is shown, with an IRC/non‐IRC ratio that correlates to this relative fraction. 相似文献
74.
75.
76.
77.
78.
79.
80.