全文获取类型
收费全文 | 2440篇 |
免费 | 388篇 |
国内免费 | 372篇 |
专业分类
化学 | 1885篇 |
晶体学 | 25篇 |
力学 | 12篇 |
综合类 | 7篇 |
数学 | 40篇 |
物理学 | 1231篇 |
出版年
2024年 | 7篇 |
2023年 | 34篇 |
2022年 | 41篇 |
2021年 | 56篇 |
2020年 | 106篇 |
2019年 | 84篇 |
2018年 | 59篇 |
2017年 | 64篇 |
2016年 | 102篇 |
2015年 | 89篇 |
2014年 | 95篇 |
2013年 | 185篇 |
2012年 | 144篇 |
2011年 | 132篇 |
2010年 | 99篇 |
2009年 | 145篇 |
2008年 | 141篇 |
2007年 | 219篇 |
2006年 | 136篇 |
2005年 | 85篇 |
2004年 | 101篇 |
2003年 | 148篇 |
2002年 | 116篇 |
2001年 | 173篇 |
2000年 | 114篇 |
1999年 | 81篇 |
1998年 | 78篇 |
1997年 | 76篇 |
1996年 | 52篇 |
1995年 | 50篇 |
1994年 | 41篇 |
1993年 | 28篇 |
1992年 | 25篇 |
1991年 | 19篇 |
1990年 | 22篇 |
1989年 | 5篇 |
1988年 | 7篇 |
1987年 | 4篇 |
1986年 | 4篇 |
1985年 | 3篇 |
1984年 | 6篇 |
1981年 | 2篇 |
1980年 | 2篇 |
1979年 | 3篇 |
1978年 | 6篇 |
1977年 | 3篇 |
1973年 | 1篇 |
1972年 | 2篇 |
1971年 | 1篇 |
1970年 | 1篇 |
排序方式: 共有3200条查询结果,搜索用时 15 毫秒
81.
Rafael Ferragut 《Physica B: Condensed Matter》2012,407(14):2676-2683
A positron annihilation spectroscopy analysis method to obtain a quantitative determination of the chemical composition around defects inside nanoparticles is presented here. This methodology is applied to AlCuMg alloys to study the rapid hardening phenomena associated with solute-vacancy aggregation. Coincidence Doppler Broadening (CDB) and lifetime spectroscopy measurements of reference samples of pure elements with and without defects were analyzed to give quantitative information of the average chemical environment around vacancies, i.e. the atomic fraction of the first neighbors of these defects, in the alloys studied. The accuracy and reproducibility of the methodology is confirmed not only by good fits to the experimental data but, in most cases, by the consistency between the mean lifetime values predicted, using the CDB estimation, and the mean lifetime values independently measured. Discrepancies in the methodology are expected when there is poor CDB contrast between elements, i.e. having similar electronic structure (for example, Al and Mg). The criterion for establishing the statistical accuracy of the separation of elements in these special cases is discussed. The methodology can be applied not only to study homogeneous materials as metallic alloys, but also to study the depth profile in thin films. 相似文献
82.
The geometries of Mg n Ni 2(n = 1-6) clusters are studied by using the hybrid density functional theory(B3LYP) with LANL2DZ basis sets.For the ground-state structures of Mg n Ni 2 clusters,the stabilities and the electronic properties are investigated.The results show that the groundstate structures and symmetries of Mg clusters change greatly due to the Ni atoms.The average binding energies have a growing tendency while the energy gaps have a declining tendency.In addition,the ionization energies exhibit an odd-even oscillation feature.We also conclude that n = 3,5 are the magic numbers of the Mg n Ni 2 clusters.The Mg 3 Ni 2 and Mg 5 Ni 2 clusters are more stable than neighbouring clusters,and the Mg 4 Ni 2 cluster exhibits a higher chemical activity. 相似文献
83.
在相对论有效原子实势近似下,用密度泛函理论方法,对Pdn(n=2,3,4),Yn(n=2,3,4),PdnY(n=1,2,3,4),PdYn(n=2,3,4),Pd2 Yn(n=2,3,4)团簇的各种可能的几何构型进行全优化计算,得到它们的基态结构和 光谱性质.结果表明,由于 Jahn-Teller效应, Pd4和Y4的基态结 构为Cs构型,P d3和Y3为C2v 构型;混合微团簇Pd3Y,Pd 4Y,PdY3,PdY4 和 Pd2Y4基态为Cs构型.最后计算了团簇的能级分布和最 高占据轨道与最低空轨道之间的能级间隙,分析了团簇的化学活性.
关键词:
Pd-Y团簇
有效原子实势
密度泛函 相似文献
84.
Configurations, stabilities and adsorption mechanisms of ground-state MonN and MonN2 (n?=?1–8) clusters are calculated by using the density functional method within the PBE level. Evidently, N atoms tend to approach more Mo atoms. Doping with two N impurity prefers to occupy symmetrical position of the host Mon (n?=?1–8) cluster except for Mo2N2 clusters. Mo4N, Mo6N, Mo2N2, Mo4N2 and Mo6N2 clusters have higher structural stabilities than their neighbors by the second derivative of total binding energy. Mo2N, Mo4N and Mo7N, Mo2N2, Mo5N2 and Mo7N2 clusters have higher kinetic reactivity than their neighbors by the HOMO–LUMO gaps. The adsorption capacity of a N atom to Mo4 cluster is stronger than the other Mo–N clusters. 相似文献
85.
Classical (Heisenberg) simulations show that the total magnetization of the lowest-energy states of clusters made of antiferromagnetically
coupled chromium atoms is planar, rather than collinear, depending on the arrangement of the atoms. Although the model Hamiltonian
is not restrictive, many cluster configurations of various numbers of atoms do not use all three directions for the spins.
This result confirms the conclusion drawn from the local-spin DFT calculation by Kohl and Bertsch that clusters of N≤13 have non-collinear magnetic moments. The present simulations show non-collinear spin ordering also for bigger clusters,
designed to be as spherical as possible following the bcc arrangement, when atoms interact both with the nearest and next-nearest neighbours. Depending on the signs of the coupling
constants frustration appears. The advantage of the discrete model, despite the simplicity, is that very large clusters and
magnetization at finite temperatures can be studied. This model predicts that clusters with specific numbers of atoms interacting
only with the nearest neighbours have collinear spins as in the bulk. We also apply the model to simulate the destruction
of the anti-ferromagnetic ordering by thermal fluctuations. This model shows no unique magnetization of mixed Fe
0.33
Cr
0.67, which is consistent with experimental observations. 相似文献
86.
与以往试验及模拟计算方法不同,文章利用从头计算分子动力学研究了液态Ga, In及Ga-In合金的偏结构. 发现合金偏双体相关函数gGaGa(r), gInIn(r)的第一峰的位置分别与液态纯Ga和纯In的第一峰 位置接近, gGaIn(r)第一峰位置大于纯Ga和纯In第一峰位置的平均值,说明液态Ga-In合金中异类原子 呈现排斥倾向, Ga-Ga, In-In团簇更容易出现.在纯Ga, 纯In中占据最高含量的1311键对在液态合金中占主导 地位,说明Ga-Ga, In-In团簇共存于液态Ga-In合金中. Voronoi多面体分析发现,随着In含量的增加, 在Ga100-xInx(30 ≤x≤qslant 50 at.% ) 区域内, Ga原子周围主配位数出现突变,由12降为10,证明Ga-Ga和In-In团簇倾向于分离.该研究结果不同于 通常的微观不均匀模型,揭示了液态Ga-In合金中团簇分离的机制. 相似文献
87.
Protein environmental effects on iron‐sulfur clusters: A set of rules for constructing computational models for inner and outer coordination spheres 下载免费PDF全文
The structural properties and reactivity of iron‐sulfur proteins are greatly affected by interactions between the prosthetic groups and the surrounding amino acid residues. Thus, quantum chemical investigations of the structure and properties of protein‐bound iron‐sulfur clusters can be severely limited by truncation of computational models. The aim of this study was to identify, a priori, significant interactions that must be included in a quantum chemical model. Using the [2Fe‐2S] accessory cluster of the FeFe‐hydrogenase as a demonstrative example with rich electronic structural features, the electrostatic and covalent effects of the surrounding side chains, charged groups, and backbone moieties were systematically mapped through density functional theoretical calculations. Electron affinities, spin density differences, and delocalization indexes from the quantum theory of atoms in molecules were used to evaluate the importance of each interaction. Case studies for hydrogen bonding and charged side‐chain interactions were used to develop selection rules regarding the significance of a given protein environmental effect. A set of general rules is proposed for constructing quantum chemical models for iron‐sulfur active sites that capture all significant interactions from the protein environment. This methodology was applied to our previously used models in galactose oxidase and the 6Fe‐cluster of FeFe‐hydrogenase. © 2016 Wiley Periodicals, Inc. 相似文献
88.
Ab initio molecular orbital calculations for N9, N−
9 and N+
9 isomers were carried out at the HF/ 6-31G*, B3PW91/6-31G*, B3LYP/6-31G* and MP2/ 6-31G* levels of theory. Stable equilibrium
geometric structures were determined by harmonic vibrational frequency analyses at the HF/6-31G*, B3PW91/6-31G* and B3LYP/6-31G*
levels of theory. The most stable free-radical N9 cluster is structure 1 with C
2
v
symmetry and that of anion N−
9 is structure 3 with C
s
symmetry. Only one stable structure of the N+
9 cation with C
2
v
symmetry was predicted. Their potential application as high-energy-density materials has been examined.
Received: 15 June 1999 / Accepted: 11 October 1999 / Published online: 14 March 2000 相似文献
89.
90.