全文获取类型
收费全文 | 3756篇 |
免费 | 742篇 |
国内免费 | 752篇 |
专业分类
化学 | 3434篇 |
晶体学 | 52篇 |
力学 | 42篇 |
综合类 | 54篇 |
数学 | 316篇 |
物理学 | 1352篇 |
出版年
2024年 | 8篇 |
2023年 | 37篇 |
2022年 | 61篇 |
2021年 | 83篇 |
2020年 | 136篇 |
2019年 | 117篇 |
2018年 | 111篇 |
2017年 | 99篇 |
2016年 | 162篇 |
2015年 | 160篇 |
2014年 | 206篇 |
2013年 | 327篇 |
2012年 | 271篇 |
2011年 | 256篇 |
2010年 | 234篇 |
2009年 | 269篇 |
2008年 | 281篇 |
2007年 | 271篇 |
2006年 | 281篇 |
2005年 | 237篇 |
2004年 | 249篇 |
2003年 | 201篇 |
2002年 | 127篇 |
2001年 | 109篇 |
2000年 | 117篇 |
1999年 | 105篇 |
1998年 | 85篇 |
1997年 | 79篇 |
1996年 | 80篇 |
1995年 | 84篇 |
1994年 | 75篇 |
1993年 | 51篇 |
1992年 | 57篇 |
1991年 | 59篇 |
1990年 | 30篇 |
1989年 | 28篇 |
1988年 | 21篇 |
1987年 | 12篇 |
1986年 | 11篇 |
1985年 | 12篇 |
1984年 | 10篇 |
1983年 | 5篇 |
1982年 | 13篇 |
1981年 | 7篇 |
1980年 | 2篇 |
1979年 | 4篇 |
1978年 | 4篇 |
1973年 | 2篇 |
1972年 | 1篇 |
1971年 | 1篇 |
排序方式: 共有5250条查询结果,搜索用时 296 毫秒
41.
Theoretical insight of nitric oxide adsorption on neutral and charged Pdn (n = 1–5) clusters 下载免费PDF全文
Pakiza Begum Pranjal Gogoi Bhupesh Kumar Mishra Ramesh Chandra Deka 《International journal of quantum chemistry》2015,115(13):837-845
Density functional theory (DFT) calculations within the framework of generalized gradient approximation have been used to systematically investigate the adsorption of nitric oxide (NO) molecule on neutral, cationic, and anionic Pdn (n = 1–5) clusters. NO coordinate to one Pd atom of the cluster by the end‐on mode, where the tilted end‐on structure is more favorable due to the additional electron in the π* orbital. On the contrary, in the neutral and cationic Pd2 system, NO coordinates to the bridge site of cluster preferably by the side‐on mode. Charge transfer between Pd clusters and NO molecule and the corresponding weakening of N? O bond is an essential factor for the adsorption. The N? O stretching frequency follow the order of cationic > neutral > anionic. Binding energy of NO on anionic clusters is found to be greater than those of neutral and cationic clusters. © 2015 Wiley Periodicals, Inc. 相似文献
42.
Dr. Caroline T. Saouma Wesley D. Morris Julia W. Darcy Prof. James M. Mayer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(25):9256-9260
Biological [Fe‐S] clusters are increasingly recognized to undergo proton‐coupled electron transfer (PCET), but the site of protonation, mechanism, and role for PCET remains largely unknown. Here we explore this reactivity with synthetic model clusters. Protonation of the arylthiolate‐ligated [4Fe‐4S] cluster [Fe4S4(SAr)4]2? ( 1 , SAr=S‐2,4‐6‐(iPr)3C6H2) leads to thiol dissociation, reversibly forming [Fe4S4(SAr)3L]1? ( 2 ) and ArSH (L=solvent, and/or conjugate base). Solutions of 2 +ArSH react with the nitroxyl radical TEMPO to give [Fe4S4(SAr)4]1? ( 1ox ) and TEMPOH. This reaction involves PCET coupled to thiolate association and may proceed via the unobserved protonated cluster [Fe4S4(SAr)3(HSAr)]1? ( 1‐H ). Similar reactions with this and related clusters proceed comparably. An understanding of the PCET thermochemistry of this cluster system has been developed, encompassing three different redox levels and two protonation states. 相似文献
43.
Prof. Ewald Janssens Hai Thuy Le Prof. Peter Lievens 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(43):15256-15262
The adsorption of propene on neutral gold clusters is investigated in a collision cell under a few collision conditions. The adsorption reaction is studied by pressure‐dependent kinetic measurements and delayed unimolecular dissociation of the excited Aun?propene complexes. The cluster size (n=9–25) and temperature (T=90–300 K) dependence of the propene adsorption is analyzed. Strong size dependences of the absorption reaction are observed; a larger propene adsorption probability was found for gold clusters composed of an even number of atoms. Propene binding energies are estimated by comparison of the temperature‐dependent unimolecular dissociation rates with rates obtained by using statistical RRKM modeling. The Aun–propene binding energies decrease non‐monotonously with cluster size and are in the range of 1.2–0.85 eV for n=9–25. Finally, the bonding of C3H6 on Aun is qualitatively described and similarities with the absorption of CO molecules on gold clusters are discussed. 相似文献
44.
[Cu32(H)20{S2P(OiPr)2}12]: The Largest Number of Hydrides Recorded in a Molecular Nanocluster by Neutron Diffraction 下载免费PDF全文
Dr. Rajendra S. Dhayal Jian‐Hong Liao Dr. Samia Kahlal Dr. Xiaoping Wang Dr. Yu‐Chiao Liu Dr. Ming‐Hsi Chiang Prof. Werner E. van Zyl Prof. Jean‐Yves Saillard Prof. C. W. Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(23):8369-8374
An air‐ and moisture‐stable nanoscale polyhydrido copper cluster [Cu32(H)20{S2P(OiPr)2}12] ( 1H ) was synthesized and structurally characterized. The molecular structure of 1H exhibits a hexacapped pseudo‐rhombohedral core of 14 Cu atoms sandwiched between two nestlike triangular cupola fragments of (2×9) Cu atoms in an elongated triangular gyrobicupola polyhedron. The discrete Cu32 cluster is stabilized by 12 dithiophosphate ligands and a record number of 20 hydride ligands, which were found by high‐resolution neutron diffraction to exhibit tri‐, tetra‐, and pentacoordinated hydrides in capping and interstitial modes. This result was further supported by a density functional theory investigation on the simplified model [Cu32(H)20(S2PH2)12]. 相似文献
45.
用密度泛函理论方法计算了CO分子吸附在有机配体聚乙烯吡咯烷酮poly(N-vinyl-2-pyrrolidone)(PVP)保护下的Au20团簇上的稳定构型的结构和性质。配体PVP通过物理吸附主要作用于Au20团簇的顶点位置。与Au20比较,配体的存在有利于CO的吸附和活化,其根本原因是PVP和CO在Au20表面分别作为供电子和吸电子基团产生的协同效应。中性及阴离子Au20团簇对配体和CO的吸附强度不同,前者对PVP吸附作用较强,后者对CO的吸附和活化作用较强。 相似文献
46.
A Functionalized Ag2S Molecular Architecture: Facile Assembly of the Atomically Precise Ferrocene‐Decorated Nanocluster [Ag74S19(dppp)6(fc(C{O}OCH2CH2S)2)18] 下载免费PDF全文
Yiyi Liu Bahareh Khalili Najafabadi Mahmood Azizpoor Fard Prof. Dr. John F. Corrigan 《Angewandte Chemie (International ed. in English)》2015,54(16):4832-4835
A ferrocene‐based dithiol 1,1′‐[fc(C{O}OCH2CH2SH)2] has been prepared and treated with a AgI salt to form the stable dithiolate compound [fc(C{O}OCH2CH2SAg)2]n (fc=[Fe(η5‐C5H4)2]). This is used as a reagent for the preparation of the nanocluster [Ag74S19(dppp)6(fc(C{O}OCH2CH2S)2)18] which was obtained in good yield (dppp=1,3‐bis(diphenylphosphino)propane). 相似文献
47.
Prof. Dr. Piotr Kaszyński Dr. Bryan Ringstrand 《Angewandte Chemie (International ed. in English)》2015,54(22):6576-6581
A simple method for the functionalization of closo‐borates [closo‐B10H10]2? ( 1 ), [closo‐1‐CB9H10]? ( 2 ), [closo‐B12H12]2? ( 3 ), [closo‐1‐CB11H12]? ( 4 ), and [3,3′‐Co(1,2‐C2B9H11)2]? ( 5 ) is described. Treatment of the anions and their derivatives with ArI(OAc)2 gave aryliodonium zwitterions, which were sufficiently stable for chromatographic purification. The reactions of these zwitterions with nucleophiles provided facile access to pyridinium, sulfonium, thiol, carbonitrile, acetoxy, and amino derivatives. The synthetic results are augmented by mechanistic considerations. 相似文献
48.
The recently introduced multireference equation of motion (MR-EOM) approach is combined with a simple treatment of spin–orbit coupling, as implemented in the ORCA program. The resulting multireference equation of motion spin–orbit coupling (MR-EOM-SOC) approach is applied to the first-row transition metal atoms Cr, Mn, Fe and Co, for which experimental data are readily available. Using the MR-EOM-SOC approach, the splittings in each L-S multiplet can be accurately assessed (root mean square (RMS) errors of about 70 cm?1). The RMS errors for J-specific excitation energies range from 414 to 783 cm?1 and are comparable to previously reported J-averaged MR-EOM results using the ACESII program. The MR-EOM approach is highly efficient. A typical MR-EOM calculation of a full spin–orbit spectrum takes about 2 CPU hours on a single processor of a 12-core node, consisting of Intel XEON 2.93 GHz CPUs with 12.3 MB of shared cache memory. 相似文献
49.
50.
振动气泡形成辐射场影响其他气泡的运动, 故多气泡体系中气泡处于耦合振动状态. 本文在气泡群振动模型的基础上, 考虑气泡间耦合振动的影响, 得到了均匀球状泡群内振动气泡的动力学方程, 以此为基础分析了气泡的非线性声响应特征. 气泡间的耦合振动增加了系统对每个气泡的约束, 降低了气泡的自然共振频率, 增强了气泡的非线性声响应. 随着气泡数密度的增加, 振动气泡受到的抑制增强; 增加液体静压力同样可抑制泡群内气泡的振动, 且存在静压力敏感区(1–2 atm, 1 atm=1.01325×105 Pa); 驱动声波对气泡振动影响很大, 随着声波频率的增加, 能够形成空化影响的气泡尺度范围变窄. 在同样的声条件、泡群尺寸以及气泡内外环境下, 初始半径小于5 μm 的气泡具有较强的声响应. 气泡耦合振动会削弱单个气泡的空化影响, 但可延长多气泡系统空化泡崩溃发生的时间间隔和增大作用范围, 整体空化效应增强. 相似文献