全文获取类型
收费全文 | 11435篇 |
免费 | 1590篇 |
国内免费 | 181篇 |
专业分类
化学 | 10646篇 |
晶体学 | 48篇 |
力学 | 19篇 |
综合类 | 2篇 |
数学 | 28篇 |
物理学 | 2463篇 |
出版年
2024年 | 22篇 |
2023年 | 167篇 |
2022年 | 289篇 |
2021年 | 335篇 |
2020年 | 486篇 |
2019年 | 445篇 |
2018年 | 263篇 |
2017年 | 235篇 |
2016年 | 642篇 |
2015年 | 679篇 |
2014年 | 627篇 |
2013年 | 815篇 |
2012年 | 674篇 |
2011年 | 686篇 |
2010年 | 612篇 |
2009年 | 732篇 |
2008年 | 748篇 |
2007年 | 854篇 |
2006年 | 766篇 |
2005年 | 560篇 |
2004年 | 492篇 |
2003年 | 501篇 |
2002年 | 224篇 |
2001年 | 225篇 |
2000年 | 173篇 |
1999年 | 180篇 |
1998年 | 156篇 |
1997年 | 123篇 |
1996年 | 110篇 |
1995年 | 76篇 |
1994年 | 59篇 |
1993年 | 32篇 |
1992年 | 33篇 |
1991年 | 22篇 |
1990年 | 12篇 |
1989年 | 16篇 |
1988年 | 15篇 |
1987年 | 14篇 |
1986年 | 16篇 |
1985年 | 13篇 |
1984年 | 15篇 |
1983年 | 5篇 |
1982年 | 12篇 |
1981年 | 10篇 |
1980年 | 7篇 |
1978年 | 9篇 |
1977年 | 7篇 |
1976年 | 4篇 |
1974年 | 2篇 |
1973年 | 3篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
1.
Giang Truong Nguyen Prof. Dr. Liviu Ungur 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(30):e202200227
Employing radical bridges between anisotropic metal ions has been a viable route to achieve high-performance single-molecule magnets (SMMs). While the bridges have been mainly considered for their ability to promote exchange interactions, the crystal-field effect arising from them has not been taken into account explicitly. This lack of consideration may distort the understanding and limit the development of the entire family. To shed light on this aspect, herein we report a theoretical investigation of a series of N -radical-bridged diterbium complexes. It is found that while promoting strong exchange coupling between the terbium ions, the N -radical induces a crystal field that interferes destructively with that of the outer ligands, and thus reduces the overall SMM behavior. Based on the theoretical results, we conclude that the SMM behavior in this series could be further maximized if the crystal field of the outer ligands is designed to be collinear with that of the radical bridge. This conclusion can be generalized to all exchange-coupled SMMs. 相似文献
2.
Cosmic dust and our origins 总被引:1,自引:0,他引:1
J Mayo Greenberg 《Surface science》2002,500(1-3):793-822
The small solid particles in the space between the stars provide the surfaces for the production of many simple and complex molecules. Processes involving the effects of ultraviolet irradiation of the thin (hundredth micron) mantles are shown to produce a wide range of molecules and ions also seen in comets. Some of the more complex ones inferred from laboratory experiments are expected to play an important role in the origin of life. An outline of the chemical evolution of interstellar dust as observed and as studied in the laboratory is presented. Observations of comets are shown to provide substantial evidence for their being fluffy aggregates of interstellar dust as it was in the protosolar nebula, i.e. the interstellar cloud which collapsed to form the solar system. The theory that comets may have brought the progenitors of life to the earth is summarized. 相似文献
3.
We study the propagation of the light mesons σ,ω,ρ, and a0(980) in dense hadronic matter in an extended derivative scalar coupling model. Within the scheme proposed it is possible
to unambiguously define effective density-dependent couplings at the Lagrangian level. We first apply the model to study asymmetric
nuclear matter with fixed isospin asymmetry, and then we pay particular attention to hypermatter in β-equilibrium. The equation
of state and the potential contribution to the symmetry coefficient arising from the mean-field approximation are investigated.
Received: 16 October 2001 / Accepted: 10 January 2002 相似文献
4.
Rees B. Rankin 《Surface science》2005,574(1):L1
Plane wave density functional theory has been employed to analyze the structure of alanine adlayers on the Cu(1 1 0) surface. Alanine forms (3 × 2) adlayers on Cu(1 1 0) that are closely related to the structures of glycine on the same surface. There is essentially no energy difference between the most stable racemic and enantiopure alanine adlayers. This observation implies that adsorption of racemic alanine on Cu(1 1 0) will result in a pseudoracemate adlayer. 相似文献
5.
One of the successful transformations within the field of organocatalysis, the organocatalytic asymmetric addition of nitromethane to α,β‐unsaturated aldehydes and ketones, has been studied by quantum chemical modeling. The level of accuracy of the hybrid density functional theory method B3LYP/6‐31G(d) was compared to a high level ab initio benchmark for this reaction. It is concluded that B3LYP/6‐31G(d) performs very well for this reaction type, giving good estimates of critical energies. The reaction between acrolein and nitromethane was studied in detail. The reaction mechanism revealed an intermediate oxazolidin structure, which is currently unknown. Alkyl substitution in various positions on the amine catalyst or α,β‐unsaturated carbonyl compound influences the reactivity in a predictive fashion. The iminium ion, prop‐2‐en‐iminium, is less activated towards nucleophilic attack compared to protonated acrolein. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
6.
The theoretical investigation of the image states in front of an ultrathin iron film grown on copper has been performed by means of the embedding method and a recently developed procedure for the inclusion of the image potential tail in a first principle calculation. From the electronic response to an applied electric field, the image plane position has been evaluated. This also allows one to obtain useful information about the spin dependent screening properties of the system. Exchange splitting, effective mass, and lifetime of such surface states result in good agreement with recently performed two-photon photoemission experiments [see A.B. Schmidt, M. Pickel, M. Wiemhöfer, M. Donath, M. Weinelt, Phys. Rev. Lett. 95 (2005) 107402]. 相似文献
7.
Alpeshkumar K. Malde Santosh A. Khedkar Evans C. Coutinho 《Journal of Physical Organic Chemistry》2007,20(2):151-160
Modification of peptides to produce peptidomimetics is of great interest, with the aim of designing potent, selective, and metabolically stable analogs having certain conformational properties. Organoboranes have been reported in the literature with a wide range of therapeutic applications. One of the therapeutically important class of molecules is amine‐carboxyboranes derived from amino acids by replacement of the Cα atom of an amino acid/peptide by boron. The conformational preferences of these peptides, with respect to backbone ω, ?, and ψ torsion angles, have been investigated by theoretical calculations. The amide bond in these molecules has the same geometry in the ground and transition states as the natural peptides. However, the boron isosteres of glycine and alanine peptides are less structured than their natural derivatives, but are distinguished by structures with a positive value for the ? angle, which is normally disfavored for natural peptides. This property could be used to build peptides with a geometry not usually seen in natural peptides. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
8.
M. Iuga G. Steinle-Neumann J. Meinhardt 《The European Physical Journal B - Condensed Matter and Complex Systems》2007,58(2):127-133
Athermal elasticity for some ceramic materials (α-Al2O3,
SiC (α and β phases), TiO2 (rutile and anatase),
hexagonal AlN and TiB2, cubic BN and CaF2, and monoclinic
ZrO2) have been investigated via density functional theory.
Energy-volume equation-of-state computations to obtain the zero pressure
equilibrium volume and bulk modulus as well as computations of the full
elastic constant tensor of these ceramics at the experimental zero pressure
volume have been performed. The present results for the single crystal
elasticity are in good agreement with experiments both for the aggregate
properties (bulk and shear modulus) and the elastic anisotropy. In contrast,
a considerable discrepancy for the zero pressure bulk modulus of some
ceramics evaluated from the energy-volume fit to the computational zero
pressure volume has been observed. 相似文献
9.
Details are given of a new method allowing an exact calculation of the spontaneous magnetization in the corner as well as along the edge at an arbitrary distance of the corner for a rectangular planar Ising ferromagnet. 相似文献
10.
David Loffreda 《Surface science》2006,600(10):2103-2112
Adsorption thermodynamics based on density functional theory (DFT) calculations are exposed for the interaction of several multifunctional molecules with Pt and Au(1 1 0)-(1 × 2) surfaces. The Gibbs free adsorption energy explicitly depends on the adsorption internal energy, which is derived from DFT adsorption energy, and the vibrational entropy change during the chemisorption process. Zero-point energy (ZPE) corrections have been systematically applied to the adsorption energy. Moreover the vibrational entropy change has been computed on the basis of DFT harmonic frequencies (gas and adsorbed phases, clean surfaces), which have been extended to all the adsorbate vibrations and the metallic surface phonons. The phase diagrams plotted in realistic conditions of temperature (from 100 to 400 K) and pressure (0.15 atm) show that the ZPE corrected adsorption energy is the main contribution. When strong chemisorption is considered on the Pt surface, the multifunctional molecules are adsorbed on the surface in the considered temperature range. In contrast for weak chemisorption on the Au surface, the thermodynamic results should be held cautiously. The systematic errors of the model (choice of the functional, configurational entropy and vibrational entropy) make difficult the prediction of the adsorption-desorption phase boundaries. 相似文献