全文获取类型
收费全文 | 2893篇 |
免费 | 357篇 |
国内免费 | 193篇 |
专业分类
化学 | 727篇 |
晶体学 | 7篇 |
力学 | 463篇 |
综合类 | 40篇 |
数学 | 1098篇 |
物理学 | 1108篇 |
出版年
2024年 | 2篇 |
2023年 | 41篇 |
2022年 | 86篇 |
2021年 | 70篇 |
2020年 | 107篇 |
2019年 | 82篇 |
2018年 | 90篇 |
2017年 | 108篇 |
2016年 | 110篇 |
2015年 | 73篇 |
2014年 | 152篇 |
2013年 | 185篇 |
2012年 | 149篇 |
2011年 | 157篇 |
2010年 | 163篇 |
2009年 | 177篇 |
2008年 | 205篇 |
2007年 | 170篇 |
2006年 | 155篇 |
2005年 | 179篇 |
2004年 | 158篇 |
2003年 | 142篇 |
2002年 | 97篇 |
2001年 | 92篇 |
2000年 | 63篇 |
1999年 | 52篇 |
1998年 | 50篇 |
1997年 | 48篇 |
1996年 | 39篇 |
1995年 | 26篇 |
1994年 | 26篇 |
1993年 | 17篇 |
1992年 | 18篇 |
1991年 | 21篇 |
1990年 | 17篇 |
1989年 | 8篇 |
1988年 | 17篇 |
1987年 | 10篇 |
1986年 | 14篇 |
1985年 | 9篇 |
1984年 | 13篇 |
1983年 | 4篇 |
1982年 | 7篇 |
1981年 | 9篇 |
1980年 | 8篇 |
1979年 | 5篇 |
1978年 | 4篇 |
1976年 | 2篇 |
1971年 | 2篇 |
1969年 | 1篇 |
排序方式: 共有3443条查询结果,搜索用时 250 毫秒
61.
Various computational approaches, using molecular mechanics (Amber), semiempirical (AM1), density functional (B3LYP), and various ONIOM methods, have been comparatively investigated for the structure of Escherichia coli NifS CsdB protein. The structure of the entire monomer containing 407 amino acid residues and 579 surrounding water molecules has been optimized. The full geometry optimization in the "active site-only" approach (including only active site atoms) has been found to give the largest root-mean-square (RMS) deviation from the X-ray structure; a much better agreement has been achieved by keeping the atoms leading to the backbones of some amino acids frozen in their positions in the X-ray structure. The best agreement has been attained by including the surrounding protein in the calculations using the two-layer ONIOM (B3LYP:Amber) approach. The results presented in this study conclusively demonstrate the importance of the protein/active-site interaction on the active-site structure of the enzyme. The present theoretical study represents the largest system studied at the ONIOM level to date, containing 7992 atoms, including 84 atoms in the QM region and rest in the MM region. 相似文献
62.
Roberto Acevedo Teodoro Meruane Jorge R. Letelier 《Theoretical chemistry accounts》1984,64(5):339-369
The theory of radiative transitions, in centrosymmetric complexes, is examined in great detail, within the framework of the crystal field method.In connection with radiative transitions, the current method of calculations, with and without invoking closure approximation, are considered from a purely theoretical point of view, by taking advantage of the irreducible tensor method put forward by Griffith.Explicit equations are derived throughout the course of this work to account for the vibronic electric dipole moments, associated with d-d and f-f type of excitations.At high Academy of Pedagogic Sciences, Santiago, Chile. 相似文献
63.
We formulate a Hartree–Fock‐LAPW method for electronic band structure calculations. The method is based on the Hartree–Fock–Roothaan approach for solids with extended electron states and closed core shells where the basis functions of itinerant electrons are linear augmented plane waves. All interactions within the restricted Hartree–Fock approach are analyzed and in principle can be taken into account. In particular, we obtained the matrix elements for the exchange interactions of extended states and the crystal electric field effects. To calculate the matrix elements of exchange for extended states, we first introduce an auxiliary potential and then integrate it with an effective charge density corresponding to the electron exchange transition under consideration. The problem of finding the auxiliary potential is solved by using the strategy of the full potential LAPW approach, which is based on the general solution of periodic Poisson's equation. Here, we use an original technique for the general solution of periodic Poisson's equation and multipole expansions of electron densities. We apply the technique to obtain periodic potentials of the face‐centered cubic lattice and discuss its accuracy and convergence in comparison with other methods. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002 相似文献
64.
Summary Based upon completely-optimized S0 and S1 molecular geometries the vibrational structures of S0-S1 absorption and fluorescence transitions of selected 1,3-diketonato boron complexes being differently substituted, are calculated within the Herzberg-Teller approach taking into account vibronic coupling contributions. In dependence on substituted diketone as well as on the co-ligand, the influence of vibronic coupling and the consequences of intensity borrowing on the spectral behaviour in absorption and fluorescence are found to be quite different for the studied boron complexes. Consequently, for some complexes their spectroscopic properties may be interpreted exclusively by means of the Herzberg-Teller approach. An analysis of the relevant vibrational modes is given. 相似文献
65.
This work describes an improved seed-mediated growth approach for the direct attachment and growth of mono-dispersed gold nanoparticles on nanostructured indium tin oxide (ITO) surfaces. It was demonstrated that, when the seeding procedure of our previously reported seed-mediated growth process on an ITO surface was modified, the density of gold nanospheres directly grown on the surface could be highly improved, while the emergence of nanorods was restrained. By field emission scanning electron microscopy (FE-SEM) and cyclic voltammetry, the growth of gold nanoparticles with increasing growth time on the defect sites of nanostructured ITO surface was monitored. Using a [Fe(CN)6]3−/[Fe(CN)6]4− redox probe, the increasingly facile heterogeneous electron transfer kinetics resulting from the deposition and growth of gold nanoparticle arrays was observed. The as-prepared gold nanoparticle arrays exhibited high catalytic activity toward the electrooxidation of nitric oxide, which could provide electroanalytical application for nitric oxide sensing. 相似文献
66.
Three-dimensional quantum mechanical calculations for vibrational predissociation of HeI2(B) van der Waals molecules are presented using the time-dependent wave packet technique within the golden rule approxima tion.The total and partial decay widths,lifetimes,rates and their dependence on initial vibrational states were obtained for HeI2 at low initial vibrational excited levels.Our calculations show that the calculated tota decay widths,lifetimes and rates agree well with those extrapolated from experimental data available The predicted total decay widths as a function of initial vibrational states exhibit highly nonlinear behavior.The very short propagation time (less.than 1 ps) required in the golden rule wave packet calculation is determined by the duration time of the final state inter-action between the fragments on the vibrationally deexcited adiabatic potential surface.The final state interaction between the fragments is shown to play an important role in determining the final rotational distri 相似文献
67.
With measurement uncertainty estimation accounting for all relevant uncertainty contributions, the results of measurements using the same procedure on different objects or samples may no longer be considered as being independent, and correlations have to be taken into account. For this purpose, a simple approximation for the estimation of covariances is derived and applied to the estimation of uncertainty for some basic combinations of two measurement results. This covariance estimate is also applied to the estimation of uncertainty for the mean value of the results of replicate measurements on the same object or sample.
相似文献
W. HaesselbarthEmail: Phone: +49-30-81041101Fax: +49-30-81045577 |
68.
We have calculated the positions of the avoided level crossings between (n+2)s, np states and nd, k Stark states in the Rydberg Stark states of the potassium atom with principal quantum number n comprised between 12 and 17. We have also studied the adiabatic electric field ionization thresholds for the above Rydberg
states. Both the ionization thresholds and the positions of avoided crossings have been calculated using the recently developed
Stark-adapted quantum defect orbital (SQDO) formalism. The presently reported values appear to be in very good agreement with
the available theoretical and experimental data. 相似文献
69.
The complexity of different quality standards can, in principle, be covered by different approaches and strategies. In-depth
process mapping of quality control (QC) work streams was used by the analytical laboratories of Lonza AG to show up the principle
differences in being compliant to different quality systems. The results identified two main drivers for all necessary actions:
process-related activities and infrastructure-related activities. In addition, a clear indication of the economic impact of
these driving forces was gained, which led the laboratories to decide on a process-oriented approach. This approach has the
advantage of being able to reflect the different demands of different quality assurance (QA) regulations within the same QC
organizational structure. Following the process helps avoid unnecessary efforts in analytical work and represents a very economical
approach, at the same time, providing high flexibility to react to different QA or customer demands.
Received: 5 July 2002 Accepted: 12 November 2002
Acknowledgements The process-oriented approach resulted from many, very challenging discussions for which I would like to thank the staff
of my organization (Analytics & QC), especially, the QA staff and the LIMS team.
Presented at Analytica Conference, 23–26 April 2002, Munich, Germany
Correspondence to B. Ciommer 相似文献
70.
The graphical unitary group approach has been applied in an efficient implementation of a general multireference configuration interaction (MRCI) method for use with small active molecular orbital spaces in a semiempirical framework. Gradients can be computed analytically for molecular orbitals from a closed-shell or a half-electron open-shell Hartree-Fock calculation. CPU times for single point energy and gradient calculations are reported. The code allows MRCI geometry optimizations of large molecules, as illustrated for the singlet ground state and the four lowest triplet states of fullerene C(76). 相似文献