首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   2827篇
  免费   428篇
  国内免费   335篇
化学   2143篇
晶体学   32篇
力学   13篇
综合类   7篇
数学   38篇
物理学   1357篇
  2024年   3篇
  2023年   44篇
  2022年   32篇
  2021年   47篇
  2020年   118篇
  2019年   95篇
  2018年   62篇
  2017年   75篇
  2016年   109篇
  2015年   94篇
  2014年   96篇
  2013年   196篇
  2012年   169篇
  2011年   152篇
  2010年   112篇
  2009年   170篇
  2008年   163篇
  2007年   244篇
  2006年   171篇
  2005年   108篇
  2004年   121篇
  2003年   178篇
  2002年   126篇
  2001年   170篇
  2000年   106篇
  1999年   84篇
  1998年   95篇
  1997年   90篇
  1996年   59篇
  1995年   65篇
  1994年   51篇
  1993年   35篇
  1992年   29篇
  1991年   27篇
  1990年   25篇
  1989年   12篇
  1988年   9篇
  1987年   5篇
  1986年   4篇
  1985年   3篇
  1984年   6篇
  1982年   2篇
  1981年   3篇
  1980年   3篇
  1979年   4篇
  1978年   7篇
  1977年   2篇
  1973年   2篇
  1972年   2篇
  1970年   1篇
排序方式: 共有3590条查询结果,搜索用时 0 毫秒
1.
During the past two decades, single-atom-centered medium-sized germanium clusters [M@Gen] (M=transition metals, n>12) have been extensively explored, both from theoretical perspectives and experimental gas-phase syntheses. However, the actual structural arrangements of the Ge13 and Ge14 endohedral cages are still ambiguous and have long remained an unresolved problem for experimental implementation. In this work, we successfully synthesize 13-/14-vertex Ge clusters [Nb@Ge13]3− ( 1 ) and [Nb@Ge14]3− ( 2 ), which are structurally characterized and exhibit unprecedented topologies, neither classical deltahedra nor 3-connected polyhedral structures. Theoretical analysis indicates that the major stabilization of the Ge backbones arises due to the substantial interaction of Ge 4p-AOs with the endohedral Nb 4d-AOs through three/four-center two-electron bonds with an enhanced electron density accumulated over the shortest Nb−Ge13 contact in 1 . Low occupancies of the direct two-center two-electron (2c–2e) Nb−Ge and Ge−Ge σ bonds point to a considerable degree of electron delocalization over the Ge cages revealing their electron deficiency.  相似文献   
2.
Superatoms are atomic clusters with tailored size and composition that mimic the chemistry of atoms in the periodic table. However, unlike the atoms whose chemistry is governed by their valence electron orbitals, the chemistry of superatoms is governed by their highest occupied molecular orbitals. In addition, due to their large size and non-spherical geometry, superatoms can promote unusual reactions and serve as the building blocks of cluster assembled materials with properties very different from conventional materials. This perspective highlights the unique role of superatoms in chemical and material sciences by focusing on superhalogens, which not only possess electron affinities larger than those of halogens but also can be stable when multiply charged. We discuss how these unique features of superhalogens enable noble gas atoms like argon to form chemical bonds at room temperature and zinc to exhibit an oxidation state of +3. The advantages of using superhalogens in the synthesis of water-resistant materials for solar cells, halogen-free electrolytes for solid-state batteries, and multiferroic materials are also discussed.  相似文献   
3.
The reaction of N2 with trinuclear niobium and tungsten sulfide clusters Nb3Sn and W3Sn (n=0–3) was systematically studied by density functional theory calculations with TPSS functional and Def2-TZVP basis sets. Dissociations of N−N bonds on these clusters are all thermodynamically allowed but with different reactivity in kinetics. The reactivity of Nb3Sn is generally higher than that of W3Sn. In the favorite reaction pathways, the adsorbed N2 changes the adsorption sites from one metal atom to the bridge site of two metal atoms, then on the hollow site of three metal atoms, and at that place, the N−N bond dissociates. As the number of ligand S atoms increases, the reactivity of Nb3Sn decreases because of the hindering effect of S atoms, while W3S and W3S2 have the highest reactivity among four W3Sn clusters. The Mayer bond order, bond length, vibrational frequency, and electronic charges of the adsorbed N2 are analyzed along the reaction pathways to show the activation process of the N−N bond in reactions. The charge transfer from the clusters to the N2 antibonding orbitals plays an essential role in N−N bond activation, which is more significant in Nb3Sn than in W3Sn, leading to the higher reactivity of Nb3Sn. The reaction mechanisms found in this work may provide important theoretical guidance for the further rational design of related catalytic systems for nitrogen reduction reactions (NRR).  相似文献   
4.
The tetracationic, univalent cluster compounds [{M(dmpe)}4]4+ (M=Ga, In; dmpe=bis(dimethylphosphino)ethane) were synthesized as their pf salts ([pf]=[Al(ORF)4]; RF=C(CF3)3). The four-membered ring in [{M(dmpe)}4]4+ is slightly puckered for M=Ga and almost square planar for M=In. Yet, although structurally similar, only the gallium cluster is prevalent in solution, while the indium cluster forms temperature dependent equilibria that include even the monomeric cation [In(dmpe)]+. This system is the first report of one and the same ligand inducing formation of isoelectronic and isostructural gallium/indium cluster cations. The system allows to study systematically analogies and differences with thermodynamic considerations and bonding analyses, but also to outline perspectives for bond activation using cationic, subvalent group 13 clusters.  相似文献   
5.
In this paper we perform a critical analysis of the Orch OR consciousness theory at the crossroad with the newest experimental results coming from the search for spontaneous radiation predicted by the simplest version of gravity-related dynamical collapse models. We conclude that Orch OR theory, when based on the simplest version of gravity-related dynamical collapse, is highly implausible in all the cases analyzed. We discuss the implications of our findings, the limitations, and future plans toward the development of more realistic gravity-related collapse models.  相似文献   
6.
7.
8.
We present a combined quantum chemical and molecular dynamics study of cyclic and noncyclic water n-mers ([(H2O]n, n = 2–6) at four different temperatures and showcase that the dynamics of small water clusters can reproduce the known properties of bulk water reasonably well. We investigate the making and breaking of the water clusters by computing the hydrogen bond strengths, average lifetimes, and relative stabilities, which are important to understand the complex solution dynamics. We compare the behavior of water clusters in the gas phase and in the solution phase as well as the variation in the properties as a function of cluster size and highlight the notably more interesting cluster dynamics of the water trimer when compared to the other water clusters. © 2019 Wiley Periodicals, Inc.  相似文献   
9.
The adsorption energies for single Ni atom on CuAl2O4(100) and (110) surfaces are 5.30 and 4.08 eV, respectively. The growth and aggregation of Ni can be effectively inhibited on the perfect CuAl2O4(100) surface. The adsorption of Ni on the spinel surface is accompanied by charge transfer. The interaction of Ni with CuAl2O4 surface is stronger than with the γ-Al2O3(110) surface.  相似文献   
10.
Boragermene 3 featuring a double bond between the Ge and dicoordinate B atoms has been synthesized for the first time by reacting the cyclic (alkyl)(boryl)germylene–PMe3 adduct 1 with Cl2BN(SiMe3)2 followed by reductive dehalogenation with KC8. Addition of a Lewis base (MeNHC) to 3 leads to the formation of the corresponding adduct 4 , which shows double bond character between the Ge and tricoordinate B atoms. Compound 3 undergoes hydrogenation with H2 concomitant with a complete scission of the Ge=B bond.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号