全文获取类型
收费全文 | 4360篇 |
免费 | 1429篇 |
国内免费 | 743篇 |
专业分类
化学 | 3010篇 |
晶体学 | 106篇 |
力学 | 70篇 |
综合类 | 41篇 |
数学 | 68篇 |
物理学 | 3237篇 |
出版年
2024年 | 34篇 |
2023年 | 65篇 |
2022年 | 174篇 |
2021年 | 156篇 |
2020年 | 222篇 |
2019年 | 192篇 |
2018年 | 151篇 |
2017年 | 184篇 |
2016年 | 250篇 |
2015年 | 230篇 |
2014年 | 239篇 |
2013年 | 587篇 |
2012年 | 355篇 |
2011年 | 343篇 |
2010年 | 236篇 |
2009年 | 343篇 |
2008年 | 313篇 |
2007年 | 285篇 |
2006年 | 283篇 |
2005年 | 230篇 |
2004年 | 229篇 |
2003年 | 195篇 |
2002年 | 166篇 |
2001年 | 162篇 |
2000年 | 144篇 |
1999年 | 121篇 |
1998年 | 107篇 |
1997年 | 74篇 |
1996年 | 61篇 |
1995年 | 51篇 |
1994年 | 53篇 |
1993年 | 38篇 |
1992年 | 38篇 |
1991年 | 24篇 |
1990年 | 27篇 |
1989年 | 21篇 |
1988年 | 14篇 |
1987年 | 21篇 |
1986年 | 14篇 |
1985年 | 10篇 |
1984年 | 16篇 |
1983年 | 3篇 |
1982年 | 9篇 |
1981年 | 7篇 |
1980年 | 8篇 |
1979年 | 15篇 |
1978年 | 8篇 |
1977年 | 10篇 |
1976年 | 7篇 |
1973年 | 4篇 |
排序方式: 共有6532条查询结果,搜索用时 15 毫秒
1.
《Magnetic resonance in chemistry : MRC》2003,41(6):417-430
A systematic study of the one‐bond and long‐range J(C,C), J(C,H) and J(H,H) in the series of nine bicycloalkanes was performed at the SOPPA level with special emphasis on the coupling transmission mechanisms at bridgeheads. Many unknown couplings were predicted with high reliability. Further refinement of SOPPA computational scheme adjusted for better performance was carried out using bicyclo[1.1.1]pentane as a benchmark to investigate the influence of geometry, basis set and electronic correlation. The calculations performed demonstrated that classical ab initio SOPPA applied with the locally dense Dunning's sets augmented with inner core s‐functions used for coupled carbons and Sauer's sets augmented with tight s‐functions used for coupled hydrogens performs perfectly well in reproducing experimental values of different types of coupling constants (the estimated reliability is ca 1–2 Hz) in relatively large organic molecules of up to 11 carbon atoms. Additive coupling increments were derived for J(C,C), J(C,H) and J(H,H) based on the calculated values of coupling constants within SOPPA in the model bicycloalkanes, in reasonably good agreement with the known values obtained earlier on pure empirical grounds. Most of the bridgehead couplings in all but one bicycloalkane appeared to be essentially additive within ca 2–3 Hz while bicyclo[1.1.1]pentane demonstrated dramatic non‐additivity of ?14.5 Hz for J(C,C), +16.6 Hz for J(H,H) and ?5.5 Hz for J(C,H), in line with previous findings. Non‐additivity effects in the latter compound established at the SOPPA level should be attributed to the through‐space non‐bonded interactions at bridgeheads due to the essential overlapping of the bridgehead rear lobes which provides an additional and effective non‐bonding coupling path for the bridgehead carbons and their protons in the bicyclopentane framework. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
2.
Ab initio calculations showed that the tetrachlorodibenzo-para-dioxin radical cations (TCDD RCs) with a planar structure have two steady states with asymmetric dioxin cycles. The activation barriers between these states are up to 2 kcal/mole, so that the RCs may be regarded as being structurally nonrigid within the dioxin cycle. The 2,3,7,8-TCDD RC is more stable than the 1,4,6,9-TCDD RC, the energy difference being 5.2 kcal/mole. The adiabatic ionization potential of 2,3,7,8-TCDD (7.54 eV) is 0.1 eV smaller than the corresponding potential of 1,4,6,9-TCDD. These factors account for the increased hemoproteide affinity and hence increased biological activity of 2,3,7,8-TCDD. 相似文献
3.
An assignment of the near-infrared bands in the 600–800 nm spectral region observed in magnetic circular dichroism (MCD)
spectra of high-spin ferrous haemoproteins is presented. The assignment is based on a relative energy level scheme for iron
d-electrons, a comparison of predicted and measured temperature dependences of MCD intensity, a sign of MCD bands and a group
theoretical analysis of allowed transitions. The proposed assignment is consistent with the ∼15-nm red shift of the ∼760 nm
band on breakage of the Fe-His bond in deoxy-myoglobin at low pH, with low-temperature photolysis experiments available for
CO complexes of several haemoproteins. In accordance with the observations, the intensity of the MCD bands for proteins with
a sulphur anion of cysteine as proximal haemligand (cytochrome P450 and chloroperoxidase) is predicted to be diminished by
at least one order of magnitude compared to that for proteins with an imidazole of a histidine as a protein-derived haemligand
(i.e. myoglobin, haemoglobin and horseradish peroxidase).
Received: 4 February 1997 / Accepted: 1 May 1997 相似文献
4.
5.
The hyperfine constants for muonium in elemental and binary inorganic solids suggest formation of three different families
of defect centre, with distinct electronic structures. The overall range of values, spanning nearly five orders of magnitude,
and their correlation with host properties such as band gap and electron affinity, reveal a deep-to-shallow instability which
has profound implications for the electrical properties of hydrogen impurity in electronic materials, both semiconducting
and dielectric. 相似文献
6.
M. Gutowski I. Dabkowska J. Rak S. Xu J.M. Nilles D. Radisic K.H. Bowen Jr 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2002,20(3):431-439
The photoelectron spectra (PES) of anions of uracil-glycine and uracil-phenylalanine complexes reveal broad features with
maxima at 1.8 and 2.0 eV. The results of ab initio density functional B3LYP and second order M?ller-Plesset theory calculations indicate that the excess electron occupies a
π* orbital localized on uracil. The excess electron attachment to the complex can induce a barrier-free proton transfer (BFPT)
from the carboxylic group of glycine to the O8 atom of uracil. As a result, the four most stable structures of the anion of
uracil-glycine complex can be characterized as the neutral radical of hydrogenated uracil solvated by the anion of deprotonated
glycine. The similarity between the PES spectra for the uracil complexes with glycine and phenylalanine suggests that the
BFPT is also operative in the case of the latter anionic species. The BFPT to the O8 atom of uracil may be related to the
damage of nucleic acid bases by low energy electrons because the O8 atom is involved in a hydrogen bond with adenine in the
standard Watson-Crick pairing scheme.
Received 6 April 2002 Published online 13 September 2002 相似文献
7.
Some aspects of electrical conduction through resonant states in metallic electrochemical nanowires are briefly discussed in a semi-quantitative way by means of concepts associated with electron gas, conductance quantization, and Fermi energy level. Aspects related to some experimental data are also discussed. 相似文献
8.
Dinesh Topwal U. Manju Sugata Ray S. Raj D. D. Sarma S. R. Krishnakumar M. Bertolo S. La Rosa G. Cautero 《Journal of Chemical Sciences》2006,118(1):87-92
Disordered Sr2FeMoO6 shows a drastic reduction in saturation magnetization compared to highly ordered samples, moreover magnetization as a function
of the temperature for different disordered samples shows qualitatively different behaviours. We investigate the origin of
such diversity by performing spatially resolved photoemission spectroscopy on various disordered samples. Our results establish
that extensive electronic inhomogeneity, arising most probably from an underlying chemical inhomogeneity in disordered samples, is
responsible for the observed magnetic inhomogeneity. It is further pointed out that these inhomogeneities are connected with
composition fluctuations of the type Sr2Fe1+x
Mo1-x
O6 with Fe-rich (x > 0) and Mo-rich (x < 0) regions.
Dedicated to Prof J Gopalakrishnan on his 62nd birthday. 相似文献
9.
湿度对绝缘体表面电导和气体电导有一定的影响,但通常在湿度传感器的研究中忽略了气体电导的贡献。本文通过特殊设计装置来区分表面电导和气体电导,并分别从实验和理论上进行了定性的研究。 相似文献
10.
The electron-stimulated desorption (ESD) of D− and H− ions from condensed D2O and H2O films is investigated. Three low-energy peaks are observed in the ESD anion yield, which are identified as arising from excitation of 2B1, 2A1 and 2B2 dissociative electron attachment (DEA) resonances. Additional structure is observed between 18 and 32 eV, which may be due to ion pair formation or to DEA resonances involving the 2a1 orbital. The ion yield resulting from excitation of the 2B1 resonance increases as the film is heated. We attribute the increase in the ion yield to thermally induced hydrogen bond breaking near the surface, which enhances the lifetimes of the excited states that lead to desorption. 相似文献