全文获取类型
收费全文 | 4970篇 |
免费 | 163篇 |
国内免费 | 1002篇 |
专业分类
化学 | 4479篇 |
晶体学 | 95篇 |
力学 | 46篇 |
综合类 | 6篇 |
数学 | 38篇 |
物理学 | 1085篇 |
综合类 | 386篇 |
出版年
2024年 | 21篇 |
2023年 | 275篇 |
2022年 | 156篇 |
2021年 | 163篇 |
2020年 | 147篇 |
2019年 | 117篇 |
2018年 | 122篇 |
2017年 | 161篇 |
2016年 | 115篇 |
2015年 | 125篇 |
2014年 | 200篇 |
2013年 | 276篇 |
2012年 | 351篇 |
2011年 | 311篇 |
2010年 | 272篇 |
2009年 | 395篇 |
2008年 | 416篇 |
2007年 | 386篇 |
2006年 | 334篇 |
2005年 | 277篇 |
2004年 | 262篇 |
2003年 | 167篇 |
2002年 | 130篇 |
2001年 | 118篇 |
2000年 | 111篇 |
1999年 | 99篇 |
1998年 | 96篇 |
1997年 | 80篇 |
1996年 | 78篇 |
1995年 | 58篇 |
1994年 | 51篇 |
1993年 | 36篇 |
1992年 | 26篇 |
1991年 | 37篇 |
1990年 | 27篇 |
1989年 | 18篇 |
1988年 | 24篇 |
1987年 | 14篇 |
1986年 | 6篇 |
1985年 | 9篇 |
1984年 | 11篇 |
1983年 | 4篇 |
1982年 | 7篇 |
1981年 | 3篇 |
1980年 | 11篇 |
1979年 | 8篇 |
1978年 | 4篇 |
1977年 | 7篇 |
1973年 | 4篇 |
1967年 | 2篇 |
排序方式: 共有6135条查询结果,搜索用时 31 毫秒
11.
J. T. Hoeft M. Polcik D. I. Sayago M. Kittel R. Terborg R. L. Toomes J. Robinson D. P. Woodruff M. Pascal G. Nisbet C. L. A. Lamont 《Surface science》2003,540(2-3):441-456
The local adsorption geometry of CO adsorbed in different states on Ni(1 0 0) and on Ni(1 0 0) precovered with atomic hydrogen has been determined by C 1s (and O 1s) scanned-energy mode photoelectron diffraction, using the photoelectron binding energy changes to characterise the different states. The results confirm previous spectroscopic assignments of local atop and bridge sites both with and without coadsorbed hydrogen. The measured Ni–C bondlengths for the Ni(1 0 0)/CO states show an increase of 0.16 ± 0.04 Å in going from atop to bridge sites, while comparison with similar results for Ni(1 1 1)/CO for threefold coordinated adsorption sites show a further lengthening of the bond by 0.05 ± 0.04 Å. These changes in the Ni–CO chemisorption bondlength with bond order (for approximately constant adsorption energy) are consistent with the standard Pauling rules. However, comparison of CO adsorbed in the atop geometry with and without coadsorbed hydrogen shows that the coadsorption increases the Ni–C bondlength by only 0.06 ± 0.04 Å, despite the decrease in adsorption energy of a factor of 2 or more. This result is also reproduced by density functional theory slab calculations. The results of both the experiments and the density functional theory calculations show that CO adsorption onto the Ni(1 0 0)/H surface is accompanied by significant structural modification; the low desorption energy may then be attributed to the energy cost of this restructuring rather than weak local bonding. 相似文献
12.
Hong-Chao Ma 《Applied Surface Science》2006,252(24):8593-8597
In this paper, we found that boron deposited on the surface of support when sodium borohydride used as reducing agent during the preparation of Pt/C catalyst. The deposition of boron markedly reduces particle size of Pt, raises electrochemical active surface (EAS) area of catalyst and electrochemical activity for hydrogen evolution or oxygen reduction reaction (ORR) compared with which prepared using other reducing agents (hydrogen and formaldehyde). 相似文献
13.
The rotational spectra of three low-energy conformers of thiodiglycol (TDG) (HOCH2CH2SCH2CH2OH) have been measured in a molecular beam using a pulsed-nozzle Fourier-transform microwave spectrometer. To determine the likely conformational structures with ab initio approach, conformational structures of 2-(ethylthio)ethanol (HOEES) (CH3CH2SCH2CH2OH) were used as starting points together with the consideration of possible intramolecular hydrogen bonding in TDG. Three lower-energy conformers have been found for TDG at the MP2=Full/6311G** level and ab initio results agree nicely with experimentally determined rotational constants. In addition, Stark measurements were performed for two of the three conformers for dipole moment determinations, adding to our confidence of the conformational structure matches between experimental observations and ab initio calculations. Of the three lower-energy conformers, one displays a compact folded-like structure with strong hydrogen bonding between the two hydroxyl groups and the central sulfide atom. Two other conformers have relatively open chain-like structures with hydrogen bonding between each of the hydroxyl groups to the central sulfur atom, of which one has pure b-type dipole moment according to the ab initio results. 相似文献
14.
P. C. Chen 《中国化学会会志》1995,42(5):755-760
Three ab initio calculations (HF/6-3IG, HF/6-3IG*, and HF/6-3IG**) on 2,4,6-trinitrotoluene were made, The results compare well with xray data, except dihedral angles of NO2 relative to the plane of the benzene ring. The deviations are attributed to packing forces and steric effects in the crystal. The most stable structure was a torsional angle 10° of the methyl top with the benzene ring, unlike toluene. The rotational barriers of the methyl top and the 4-nitro group are small. Hydrogen bonding, dipole moments and total atomic charges arc calculated. 相似文献
15.
The FRS-ESR facility at GSI provides one of the most efficient methods for direct mass measurements. In the present experiment,
exotic nuclei were produced via fragmentation of 152Sm projectiles in a thick beryllium target at 500-600 MeV/u, separated in-flight with the fragment separator FRS, and injected
into the storage-cooler ring ESR. Time-resolved Schottky Mass Spectrometry was applied for mass measurements of stored and
electron-cooled bare and few-electron ions. 373 different nuclides were identified by means of the spectra of their revolution
frequencies. Masses for 18 nuclides (84Zr, 92Ru, 94Rh, 107,108,110Sb, 111,112,114I, 118Ba, 122,123La, 124Ce, 127Pr, 129Nd, 132Pm, 134Sm, 137Eu) have been determined for the first time. Masses for 111,112I and 113Xe have been obtained via known α-decay energies. The experiment and first results will be presented. 相似文献
16.
苝二酸酐与嘧啶衍生物的氢键组装 总被引:1,自引:0,他引:1
用半经验AM1方法对苝二酸酐与嘧啶衍生物的1:1及1:2氢键复合物进行理论研究,表明随着氢键数目增多,弱相互作用能变大,主体上的供电基和客体上的吸电基有利于氢键相互作用,氢键导致电子从主体流向客体.用INDO/SCI方法计算配合物的电子光谱,表明其长波吸收峰与主体相比发生兰移,各配合物的长波吸收峰位置相差不大,与实验一致.讨论吸收峰兰移的原因并对电子跃迁进行理论指认,同时得到了配合物的双质子转移势能曲线,给出了相对于N-H键的过渡态和活化能. 相似文献
17.
A. Borgschulte R. Gremaud S. de Man R.J. Westerwaal J.H. Rector B. Dam R. Griessen 《Applied Surface Science》2006,253(3):1417-1423
The optical properties, the switching kinetics and the lifetime of hydrogen switchable mirrors based on Mg-Ni alloys are determined with particular regard to the composition of the optically active metal-hydride layer in combination with the thickness of the catalytic capping layer. For this, a high-throughput experiment is introduced. The switching kinetics and the reversibility of switchable mirrors are strongly thickness dependent, though the details hinge on the fine structure of the clustered capping layer. Therefore, the kinetics is correlated with the surface structures of Pd on MgyNi1−y as investigated by scanning tunneling microscopy. The results are explained by the so-called strong metal-support interaction (SMSI) state, characterized by a complete encapsulation of the capping layer clusters by oxidized species originating from the support. The SMSI-effect is less important with increasing Pd-layer thickness, and is suppressed by a good wetting of the Pd-clusters on the optically active film. This explains the critical thickness for the catalyzed hydrogen uptake observed in many switchable mirror systems. Moreover, the degradation of the kinetics during cycling is found to depend on the Pd-layer thickness and on the gas environment. Only films, covered with at least 15 nm Pd, show small degradation caused by the SMSI-effect. The SMSI-effect is partly reversible: after changing the gas environment from hydrogen to oxygen, the oxide on the Pd-clusters can be partly removed. 相似文献
18.
R_FN(O )R_F和R_FNO的F113溶液在室温下与一系列的对位取代苯甲醛反应,得到稳定的对位取代苯甲酰基全氟烷基氮氧自由基。由△a_N和△a_F~β的σ单参数相关以及△a_N与σ和σ 双参数相关表明:极性效应是影响氟烷基酰基氮氧自由基中氮原子自旋密度变化的主要因素,而自旋离域效应的影响是很小的。 相似文献
19.
The nature of hydrologic parameters in reservoir management models is uncertain. In mathematical programming models the uncertainties are dealt with either indirectly (sensitivity analysis of a deterministic model) or directly by applying a chance-constrained type of formulation or some of the stochastic programming techniques (LP and DP based models). Various approaches are reviewed in the paper. Moran's theory of storage is an alternative stochastic modelling approach to mathematical programming techniques. The basis of the approach and its application is presented. Reliability programming is a stochastic technique based on the chance-constrained approach, where the reliabilities of the chance constraints are considered as extra decision variables in the model. The problem of random event treatment in the reservoir management model formulation using reliability programming is addressed in this paper. 相似文献
20.
Schiff碱水杨醛苯甲酰腙的特性 总被引:3,自引:1,他引:2
研究了 Schiff碱水杨醛苯甲酰腙 (简称 SBH)晶体在 DMSO及其 DMSO- H2 O的混合溶剂中的红外光谱 ,通过 SBH氘代前后的 IR对比发现 ,羟基氢质子与混合溶剂 DMSO- H2 O(3∶ 1 ,V/ V)产生较大的相互作用。向溶有 SBH的 75 % DMSO- 2 5 % H2 O的溶液滴加 KOH发现 ,SBH分子上的 C O羰基基团先与 KOH作用 ,其后与 O H 羟基基团作用 相似文献