全文获取类型
收费全文 | 3272篇 |
免费 | 566篇 |
国内免费 | 932篇 |
专业分类
化学 | 2423篇 |
晶体学 | 28篇 |
力学 | 245篇 |
综合类 | 34篇 |
数学 | 127篇 |
物理学 | 1913篇 |
出版年
2024年 | 24篇 |
2023年 | 58篇 |
2022年 | 115篇 |
2021年 | 134篇 |
2020年 | 130篇 |
2019年 | 150篇 |
2018年 | 118篇 |
2017年 | 148篇 |
2016年 | 167篇 |
2015年 | 140篇 |
2014年 | 185篇 |
2013年 | 258篇 |
2012年 | 279篇 |
2011年 | 295篇 |
2010年 | 191篇 |
2009年 | 235篇 |
2008年 | 215篇 |
2007年 | 230篇 |
2006年 | 176篇 |
2005年 | 176篇 |
2004年 | 173篇 |
2003年 | 149篇 |
2002年 | 120篇 |
2001年 | 115篇 |
2000年 | 116篇 |
1999年 | 106篇 |
1998年 | 103篇 |
1997年 | 67篇 |
1996年 | 59篇 |
1995年 | 52篇 |
1994年 | 48篇 |
1993年 | 41篇 |
1992年 | 43篇 |
1991年 | 24篇 |
1990年 | 19篇 |
1989年 | 16篇 |
1988年 | 11篇 |
1987年 | 13篇 |
1986年 | 7篇 |
1985年 | 16篇 |
1984年 | 2篇 |
1983年 | 6篇 |
1982年 | 11篇 |
1981年 | 2篇 |
1980年 | 3篇 |
1979年 | 13篇 |
1978年 | 3篇 |
1977年 | 2篇 |
1976年 | 2篇 |
1973年 | 4篇 |
排序方式: 共有4770条查询结果,搜索用时 31 毫秒
91.
Hassan Rabaâ Bernd Engels Thomas Hupp A. Stephen K. Hashmi 《International journal of quantum chemistry》2007,107(2):359-365
A general scheme for the endo‐ and exo‐cyclization of furan reactivity with [L ‐AuIII, IClx] with (x = 3, 1 and L ‐acetylene and vinylidene) complexes is investigated using density functional theory (DFT) code. Two conceivable mechanisms via a [4 + 2] Diels–Alder process or carbene complex are analyzed. According to the activation energy values of the gold (III and I) catalyst, the first mechanism, which implies the Diels–Alder reaction of AuIII, is thermodynamically favored and gives more evidence of the intramolecular addition of the furan with the alkynes. The second mechanism, presumably assisted by the spontaneous formation of the exo‐vinylidene complexes and intermediates of gold (III, I) by forming the carbene complex, is kinetically favored. Additionally, we compare our results with other structures with intramolecular additions that exhibit the quasi‐similarity of gold analogue structures. Differences in activation energies are observed, according to the functional used. Finally, we probe the solvent effects, which decrease the energy barrier in the path. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
92.
Summary Methylbenzenes, pyridines and pyrazines were investigated on fused-silica and glass capillary columns coated with SE-30 and
PEG-40M/KF liquid phases, at two temperatures, 80° and 110°C. The contribution of the methylene groups to the partial molar
free sorption energy was determined for methylpyridines and pyrazines. Equations are proposed for the calculation of the retention
indices of methyl pyridines and pyrazines. These equations are based on the ortho- and α-effects of the methyl groups. The
predicted indices have been experimentally tested for six dimethyl- and trimethylpyridines, and four methylpyrazines. Good
accuracy of the calculation permits to use this method for the identification of methylpyridines and pyrazines in complex
mixtures.
Enlarged text of the paper presented at the Eighth International Symposium on Capillary Chromatography, Riva del Garda, Italy,
May 19–21, 1987. 相似文献
93.
Charge calculations in molecular mechanics. Part 8 Partial atomic charges from classical calculations 总被引:1,自引:0,他引:1
Raymond J. Abraham Guy H. Grant Ian S. Haworth Paul E. Smith 《Journal of computer-aided molecular design》1991,5(1):21-39
Summary The CHARGE2 programme, which involves the classical calculation of both the inductive and resonance contributions to the partial atomic charges in molecules is described, and the charges and electrostatic potentials obtained presented for some illustrative examples.In substituted methanes (CH3X, CF3X, CCl3X) the effects of varying the electronegativity of the substituents and the - and -substituent contributions are clearly illustrated for a variety of substituent groups X.The problems involved in the inclusion of silicon into this scheme are detailed, together with the methods of overcoming them. The partial atomic charges ( and contributions) and electrostatic potentials for some silicon oxygen compounds are presented and discussed.The partial atomic charges from CHARGE2 for all the natural amino acids as their N-acetyl, N-methyl-amides are given and compared with those obtained from the AMBER and ECEPP/2 force fields. Considerable differences in these figures are observed, with the AMBER charges consistently much larger than those from the other two methods.The CHARGE2 partial atomic charges and electrostatic potentials for the four common nucleic acids, adenine, cytosine, guanine and thymine, are given and compared with those derived from other calculations. Again there is general similarity but also there are considerable differences, with those from the AMBER force field somewhat larger than the other methods.For previous parts in this series, see Refs. 1-7. 相似文献
94.
Traceability of the measurement of analytical parameters capable of evaluating the performance of methods is an important
concept for the assessment of quality for the routine control, especially for residue monitoring of non-authorized medicinal
substances in food from animal origin. The European Decision no. 657/2002/EC recommends to calculate two statistical limits,
CCα and CCβ, which allow to evaluate the critical concentrations above which the method reliably distinguish and quantify
a substance taking into account the variability of the method and the statistical risk to take a wrong decision. The calculation,
which can be derived from the ISO standard no. 11843 is applied on a routine basis. An example displays a very simple way
for evaluating the performance of an LC-MSMS method which has been validated a few years ago and is qualified onto a Micromass
Quattro LCZ tandem mass spectrometer to monitor and confirm the nitrofuran metabolite residues in food from animal origin.
Community Reference Laboratory for Antimicrobial Veterinary Drug Residue Control in Food from Animal Origin 相似文献
95.
Yuji Naruse Atsushi Takamori Itsuki Nagasawa 《Phosphorus, sulfur, and silicon and the related elements》2020,195(7):523-525
AbstractWe previously designed and prepared the first molecules to exhibit observable CD spectra by n-σ* excitation, 2,6-dithiaspiro[3.3]heptane 2,6-dioxide. Spiro[3.3]heptane frameworks possess axial asymmetry due to puckering of 2 four-membered rings; the ring bonds are rich in p-character due to acute bond angles, which lowers the σ* energy levels. In contrast, the lone pairs are rich in s-character, which results in a good donor with conformational fixation. We expected that, instead of lone pairs as donating orbitals, the use of σ-electron-donating Si-Si bonds should result in UV absorption in the observable range (>180?nm), so that the Cotton effect could appear, at least partially, in that range. We designed 2,6-disilyl-2,6-disilaspiro[3.3]heptanes as models, and performed theoretical calculations to confirm our idea. 相似文献
96.
The reaction path, the dynamical properties along the reaction path and CVT rate constants are computed by the ab initio MO method, the reaction path Hamiltonian theory and the variational transition state theory. The results show that the effect of the electron correlation energy on activation barrier is large, the recrossing and tunneling effects exist in the reaction. 相似文献
97.
N. Nandi D. Vollhardt R. Rudert 《Colloids and surfaces. A, Physicochemical and engineering aspects》2004,250(1-3):279-287
In the present work, the pair potential of enantiomeric N-palmitoyl aspartic acid amphiphile monolayer at the air/water interface is calculated based on an atomistic model. The molecular structure and partial charges are calculated using two semi empirical (PM3, AM1) and one empirical (Gasteiger and Marcili) methods. A distance-dependent dielectric function is used to represent the interfacial dielectric constant at the aqueous subphase. The present study indicates that a pair of molecules have favorable interaction at specific ranges of mutual orientations. Other orientations are favorable but at larger separations. Favorable electrostatic interaction at a specific combination of orientation and short separations of the head groups significantly contribute to the total energy. The curvature of the domain boundary is suggested to be driven by the favorable arrangement which is dependent on the pair potential of molecules. The use of charges obtained by the PM3 and GM do not lead to a significant variation of the orientation-dependent features, while the AM1 predicts higher partial charges and interactions are stronger than the former two methods. However, orientation-dependent features remain the same. The variations in the LJ parameters and charges indicate that the conclusions made are insensitive to the choice of parameters. The mutual favorable interaction predicted by calculation agree with the handedness of curvature of domains. 相似文献
98.
99.
邻氯苄基氯与锡反应合成三(邻氯苄基)氯化锡,经x射线方法测定了新化合物 的晶体结构,化合物属三方晶系,空间群为R-3,晶体学参数:α=b=1.3583(4) mn,c=2.1147(8)am,v=3.3790(19)nm~3,Z=6,μ(Mo kα)=16.11cm~-1, r (000):1572,R_1=O.0755;Sn-C键长分别为0.2148(13)和0.220(2)nm,Sn-C1 键为0.2528(15)和0.2477(13)Bill.中心锡原子与亚甲基碳和氯原子构成畸型四 面体.并对其结构进行量子化学从头计算,探讨化合物的稳定性、分子轨道能量、 原子净电荷布居规律以及一些前沿分子轨道的组成特征. 相似文献
100.
严继民 《中国科学B辑(英文版)》1990,(7)
An ab initio calculation of the hydrogen bond complex (HF)_2 is given with the 6-311 G~(**) basis set, according to which the potential surface around the balance point of the distancès and the orientations between two HF molecules is obtained. The atomic charges in the system are calculated with the PD/LSF method (potential-derived/least-square-fitting method) and then an analysis of the hydrogen bond interaction between two HF molecules is given with the (exp-6-1) potential function, by means of which it is shown that the main interaction between them is not an electro-static but a charge transfer one. The potential curve between two HF molecules is like a Morse function. 相似文献