全文获取类型
收费全文 | 995篇 |
免费 | 65篇 |
国内免费 | 256篇 |
专业分类
化学 | 531篇 |
晶体学 | 1篇 |
力学 | 68篇 |
数学 | 206篇 |
物理学 | 345篇 |
综合类 | 165篇 |
出版年
2024年 | 1篇 |
2023年 | 21篇 |
2022年 | 20篇 |
2021年 | 25篇 |
2020年 | 33篇 |
2019年 | 24篇 |
2018年 | 15篇 |
2017年 | 18篇 |
2016年 | 18篇 |
2015年 | 30篇 |
2014年 | 42篇 |
2013年 | 69篇 |
2012年 | 46篇 |
2011年 | 42篇 |
2010年 | 52篇 |
2009年 | 81篇 |
2008年 | 96篇 |
2007年 | 89篇 |
2006年 | 65篇 |
2005年 | 50篇 |
2004年 | 52篇 |
2003年 | 44篇 |
2002年 | 33篇 |
2001年 | 33篇 |
2000年 | 26篇 |
1999年 | 29篇 |
1998年 | 31篇 |
1997年 | 29篇 |
1996年 | 28篇 |
1995年 | 23篇 |
1994年 | 17篇 |
1993年 | 12篇 |
1992年 | 15篇 |
1991年 | 21篇 |
1990年 | 3篇 |
1989年 | 12篇 |
1988年 | 17篇 |
1987年 | 15篇 |
1986年 | 11篇 |
1985年 | 4篇 |
1984年 | 8篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1981年 | 6篇 |
1980年 | 3篇 |
1979年 | 1篇 |
1977年 | 1篇 |
1973年 | 1篇 |
1972年 | 1篇 |
排序方式: 共有1316条查询结果,搜索用时 0 毫秒
11.
Wolfgang Quapp 《Theoretical chemistry accounts》1989,75(6):447-460
Gradient extremals are curves in configuration space denned by the condition that the gradient of the potential energy is an eigenvector of the Hessian matrix. Solutions of a corresponding equation go along a valley floor or along a crest of a ridge, if the norm of the gradient is a minimum, and along a cirque or a cliff or a flank of one of the two if the gradient norm is a maximum. Properties of gradient extremals are discussed for simple 2D model surfaces including the problem of valley bifurcations. 相似文献
12.
本文用变分过渡态理论,首次对无鞍点的释能反应O+CS→CO+S、O+CO→CO+O和S+CS→CS+S进行了动力学研究,考察了反应动力学瓶颈区性质,计算了反应的速度常数,并将O+CS反应的速度常数值与实验值及经典轨迹计算结果进行了比较,三者基本相符. 相似文献
13.
M.E. Kletskii A.A. Millov A.V. Metelitsa M.I. Knyazhansky 《Journal of photochemistry and photobiology. A, Chemistry》1997,110(3):857-270
The mechanism of light-induced transformation in the salicylideneaniline molecule was studied by semiempirical PM3 calculations. The structures and energies of the minima and saddle points (transition states) on the S0, S1 and T1 potential energy hypersurfaces (PESs) were obtained, together with the gradient lines on the PESs. The structure-energy scheme was compared with the experimental findings. According to the results obtained, the following principle processes are observed: fast S1 excited state intramolecular proton transfer (ESIPT), followed by typical ESIPT fluorescence; the formation of two S1 twisted intramolecular charge transfer (TICT) structures which quench the ESIPT fluorescence; the diabatic formation of two ground state metastable coloured “post-TICT” structures responsible for photochromism. 相似文献
14.
15.
采用Hartree-Fock和MP2方法在多种水平下优化了(H2O)^+n(n =1,2)的几何结构,并进行了振动光谱分析。结果表明:对(H2O)^+采用MP2/6-311++G(d,p)可得出最满意的结论。 相似文献
16.
应用改进了的旋转全电极上的电势阶跃计时库仑法,分别测定了不同电极电势下氧还原过程中电极吸附中间物和溶解中间物氧化所需的电量,实验证明,在此过程中电极上确有吸附中间物存在,而且是电极电势的函数,但其分子属性尚需进一步鉴别。 相似文献
17.
Stephen P. Walch 《中国化学会会志》1995,42(2):221-231
Computed potential energy surfaces are often required for computation of such observables as rate constants as a function of temperature, product branching ratios, and other detailed properties. We have found that computation of the stationary points/reaction pathways using CASSCF/derivative methods, followed by use of the internally contracted CI method with the Dunning correlation consistent basis sets to obtain accurate energetics, gives useful results for a number of chemically important systems. Applications to complex reactions leading to NOx and soot formation in hydrocarbon combustion are discussed. 相似文献
18.
Shujun Su 《Journal of Molecular Structure》1998,430(1-3):137-148
The potential energy hypersurface of the ground triplet states of the BNO-BON-NBO system has been investigated using traditional ab initio electronic structure theory. The molecules studied have the molecular formula BON and include three linear and three angular species, and two transition states for the isomerization of an angular N-B-O to an angular B-O-N and a linear B-NO, respectively. All stationary points on the BNO-BON-NBO isomerization potential energy surface have been characterized employing UMP2, UMP4, and Gaussian-2 (G2) theory with the 6-311G(d), 6-311G(2d), and TZ2P basis sets. The isomerization for an angular N-BO to the linear B-NO has a lower energy barrier than that of the former to an angular B-ON. Energetics are presented with G2 energies. Two sets of resonance structures for both bent B-NO (boron nitrosyl) and B-ON (boron isonitrosyl) were proposed and the bonding in the two species was analyzed. For the purpose of comparison, the density functional theory based hybrid methods B3LYP/6-311G(d) and B3LYP/TZ2P have also been applied to both geometry optimization and single-point calculations. It is found that the B3LYP prediction of the nature of the linear B-O is contradictory to that made by all MPn(n = 2 and 4) calculations. The cause for this contradiction is discussed. 相似文献
19.
100公里以上的大气分子离子主要为NO~+。它的辐射特点及它与电子、原子或分子的相互作用,对于理解大气的化学过程具有特别重要的意义。为了研究这些过程,确定NO~+分子离子基态及其各个激发态的分子势能函数是非常重要的。精确的X~1Σ~+,A~1Ⅱ和a~3∑~+势能曲线已发表;基于光电子谱的研究发现了NO~+的其它激发态,但对于这些激发态的研究尤其是势能函数的研究不多。本文研究并导出NO~+的基态和10个激发态的势能函数。 相似文献
20.
Bifurcations of reaction channels are related to valley-ridge inflection points and it is examined what happens when these do not coincide with transition states. Under such conditions there result bifurcating regions. There exist a number of different prototypes for such regions which are discussed explicitly on the basis of the pertinent Taylor expansions. When bifurcations occur close enough to transition states then there result bifurcating transition regions. An example for a bifurcating transition region is exhibited which is obtained from a quantum mechanical ab initio calculation for the ring opening of cyclopropylidene to aliene. In general there exist no orthogonal trajectory patterns which could serve as simplified models for channel bifurcations.Operated for the U.S. Department of Energy by Iowa State University under Contract No. W-7405-ENG-82. This work was supported by the Office of Basic Energy Sciences 相似文献