全文获取类型
收费全文 | 2248篇 |
免费 | 487篇 |
国内免费 | 358篇 |
专业分类
化学 | 1207篇 |
晶体学 | 18篇 |
力学 | 348篇 |
综合类 | 14篇 |
数学 | 577篇 |
物理学 | 929篇 |
出版年
2024年 | 6篇 |
2023年 | 58篇 |
2022年 | 103篇 |
2021年 | 119篇 |
2020年 | 187篇 |
2019年 | 133篇 |
2018年 | 116篇 |
2017年 | 99篇 |
2016年 | 132篇 |
2015年 | 120篇 |
2014年 | 165篇 |
2013年 | 171篇 |
2012年 | 159篇 |
2011年 | 148篇 |
2010年 | 103篇 |
2009年 | 119篇 |
2008年 | 122篇 |
2007年 | 108篇 |
2006年 | 132篇 |
2005年 | 83篇 |
2004年 | 93篇 |
2003年 | 69篇 |
2002年 | 71篇 |
2001年 | 69篇 |
2000年 | 51篇 |
1999年 | 51篇 |
1998年 | 46篇 |
1997年 | 34篇 |
1996年 | 29篇 |
1995年 | 31篇 |
1994年 | 19篇 |
1993年 | 24篇 |
1992年 | 21篇 |
1991年 | 8篇 |
1990年 | 15篇 |
1989年 | 13篇 |
1988年 | 3篇 |
1987年 | 4篇 |
1986年 | 8篇 |
1985年 | 7篇 |
1984年 | 5篇 |
1983年 | 6篇 |
1982年 | 7篇 |
1981年 | 4篇 |
1980年 | 6篇 |
1979年 | 5篇 |
1978年 | 3篇 |
1977年 | 4篇 |
1976年 | 1篇 |
1975年 | 3篇 |
排序方式: 共有3093条查询结果,搜索用时 18 毫秒
51.
M. Baru A. Danilov I. Vagenina E. Gorbunova S. Moshnikov L. Mustaeva V. Cherskii 《Chromatographia》1997,45(1):351-354
Summary The design of new dynamic, axial-compression columns with a system for continous packed bed adjustment and monitoring of the
floating adapter position is described. The columns are meant for liquid chromatography at low pressures (up to 8 bar) in
aqueous and organic media with stationary phases of all types. The columns have adapter position pickups for continuous automatic
monitoring of the bed height (original “swellographic” monitoring). The column described with gas pressurisation was tested
with soft Sephadex G-10 and G-25. In spite of the reduction in external porosity there was no dramatic increase in back-pressure.
The column proved to provide long-term stability of the packed bed and improvement in resolution.
Presented at the 21st ISC held in Stuttgart, Germany, 15th–20th September, 1996 相似文献
52.
The results of non empirical quantum-chemical calculations using the RHF/6-31G(d) and MP2/6-31G(d) methods do not agree with
proposals for the axial position of the H atom on the N atom in the piperidine molecule. According to RHF/6-31G(d) calculations
for the N-methylpiperidine molecule and its chloro-substituted derivatives an equatorially placed methyl group is energetically
more favored than an axial. The axial C-Cl and C-H bonds in these molecules are longer than the equatorial. The 35 Cl NQR frequencies for the axial Cl atoms are lower than the equatorial. The 35 Cl NQR frequency of the axial chlorine atom in 2-chloro-1-methylpiperidine is anomalously low. This is chiefly due to the
high population density of its p σ-orbital and this is a result of the polarization of the C-Cl bond via the N atom unshared
electron pair directly through the field. The effect of a similar unshared electron pair on the parameters of the C-Cl bond
in the ClCH2NH2 molecule has been studied by the RHF/6-31(g) method for different angles of rotation of the ClCH2 group around the C-N bond.
__________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 1044–1052, July, 2005. 相似文献
53.
Cobalt(Ⅱ) can form complexes with Hdbm in different environments. Hdbm reacted with cobalt nitrate to give complex 1 [Co(dbm)2·2H2O]. When complex 1 reacted with pyridine, α-stilbazole or 4,4′-bipyridine respectively, complex 2 [Co(DBM)2Py2] (Py=pyridine), 3 [Co(DBM)2Sbz2] (Sbz=α-stilbazole) or 4 [Co(DBM)2BPy]n was obtained in turn through metathetical reaction. The coordination modes are octahedral polyhedrons. In the crystal structures, the two dbms take the plane position and two other donor molecules take the axial position. CCDC: 196070 for complex 2; 186859 for complex 3. 相似文献
54.
Chelsea N. Widener Alexandria N. Bone Mykhaylo Ozerov Rachael Richardson 路正光 Komalavalli Thirunavukkuarasu Dmitry Smirnov 陈学太 薛子陵 《无机化学学报》2020,36(6):1149-1156
最近Ruamps和同事发现三角双锥构型的Ni(Ⅱ)配合物[Ni(Me6tren)Cl]ClO4(1,Me6tren=tris(2-(dimethylamino)ethyl)amine)具有大的单轴磁各向异性(J.Am.Chem.Soc.,2013,135:3017-3026)。他们利用HF-EPR研究获得横向零场分裂(ZFS)参数E=1.56(5)cm-1但未能确定轴向零场分裂参数D。在本工作中,我们利用0~17.5 T和5 K的变磁场远红外光谱(FIRMS)来检测自旋基态S=1中的MS=±1和MS=0态之间的磁跃迁。在FIRMS中直接观察到Zeeman分裂态之间的跃迁,得出轴向ZFS参数D=-110.7(3)cm-1。我们对1的晶体结构进行了Hirshfeld表面分析,揭示了1分子中的阳离子与阴离子之间以及分子之间的相互作用。 相似文献
55.
A series of samples of increasing volume (from 0.001 to 4.0 cm3), containing the same constant concentration (40 g/l) of two simple compounds, ethylbenzoate and 4-tert.-butylphenol were injected on a Kromasil-C18 column with methanol-water (62:38. v/v) as the mobile phase. Complex band profiles were observed when the volume of the sample became large enough and strong band interference took place. The analysis of the fractions collected during the elution of the mixed band demonstrates that, for samples larger than 2 cm3, the band of 4-tert.-butylphenol is split into two separate bands, one eluted before and the other eluted after the band of ethylbenzoate. Such a phenomenon has never been observed yet in RPLC, under isocratic elution conditions. 相似文献
56.
Takashi Yokoyama Kazuhiro Ikemoto Takatsugu Kihara Kouhei Teramura Keisuke Uryu Kohji Shimizu Motoki Bitoh Kohji Matsuzaki Michio Zenki 《Journal of solution chemistry》2006,35(5):639-657
Coordination equilibrium constants (K
NiS) of some donor solvent molecules to 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecanenickel(II) ([Ni(Me4[12]aneN4)]2+) were determined in nitrobenzene (a noncoordinating bulk solvent). The first (K
NiS1) and second stepwise coordination equilibrium constants (K
NiS2) for 1,4,7,10-tetraazacyclododecanenickel(II) ([Ni([12]aneN4)]2+), 1,4,8,11-tetraazac yclotetradecane- nickel(II) ([Ni([14] aneN4)]2+), 1,4,8,11-tetrathiacyclotetra-decanenickel(II) ([Ni([14]aneS4)]2+) were also reinvestigated. The K
NiS values for [Ni(Me4[12]aneN4)]2+ were compared to those of [Ni([12]aneN4)]2+, (1R,4S, 8R,11S)-1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecanenickel(II) (R,S,R,S-[Ni(Me4[14]aneN4)]2+), R,R,S,S-[Ni(Me4[14]aneN4)]2+, [Ni([14]aneN4)]2+, and [Ni([14]aneS4)]2+. Coordination of pyridine (Py), N,N,N′,N′-tetramethylurea (TMU), and N,N-dimethylacetamide (DMA) to [Ni(Me4[12]aneN4)]2+ was observed, although these donor solvent molecules did not coordinate to R,S,R,S-[Ni(Me4[14]aneN4)]2+. The K
NiS values for Py, TMU, and DMA are 7.9, 2.8, and 9.0 dm3⋅mol−1, respectively. Some hydrogen-bonding waters were coordinated to R,S,R,S-[Ni(Me4[14]aneN4)]2+, but such waters did not coordinate to [Ni(Me4[12] aneN4)]2+. Also, the K
NiS2 values were larger than the corresponding K
NiS1 values for [Ni([14]aneS4)]2+. Furthermore, the K
NiS1 values for [Ni([12]aneN4)]2+ were the largest among these nickel(II) complex cations. The K
NiS, K
NiS1, and K
NiS2 values are discussed in terms of properties of the donor solvents and steric strains of these nickel(II) complex cations. 相似文献
57.
A sandwiched structure of CdS/Ag/ZnO nanorod photoanode exhibits greatly enhanced photoelectrochemical activity for solar hydrogen generation, due to synergistic effect of CdS nanocrystallites and plasmonic Ag nanoparticles for the enhanced optical absorption and the promoted charge carrier separation. 相似文献
58.
Tatsuhiko Kashimura Tomoya Ikezaki Yusuke Ohta Satoshi Yabushita 《Journal of computational chemistry》2019,40(2):482-499
One of the most spectacular yet unsolved problems for the ICN -band photodissociation is the non-statistical spin-rotation F1 = N + 1/2 and F2 = N − 1/2 populations for each rotation level N of the CN fragment. The F1/F2 population difference function f(N) exhibits strong N and λ dependences with an oscillatory behavior. Such details were found to critically depend on the number of open-channel product states, namely, whether both I (2P3/2) and I (2P1/2) are energetically available or not as the dissociation partner. First, in the asymptotic region, the exchange and dipole-quadrupole inter-fragment interactions were studied in detail. Then, as the diabatic basis, we took the appropriate symmetry adapted products of the electronic and rotational wavefunctions for the F1 and F2 levels at the dissociation limits. We found that the adiabatic Hamiltonian exhibits Rosen–Zener–Demkov type nonadiabatic transitions reflecting the switch between the exchange interaction and the small but finite spin-rotation interaction within CN at the asymptotic region. This non-crossing type nonadiabatic transition occurs with the probability 1/2, that is, at the diabatic limit through a sudden switch of the quantization axis for CN spin S from the dissociation axis to the CN rotation axis N . We have derived semiclassical formulae for f(N) and the orientation parameters with a two-state model including the 3A′ and 4A′ electronic states, and with a four-state model including the 3A′ through 6A′ electronic states. These two kinds of interfering models explain general features of the F1 and F2 level populations observed by Zare's group and Hall's group, respectively. © 2018 Wiley Periodicals, Inc. 相似文献
59.
The condensation of 2′-formylbiphenyl-2-carboxylic acid 4 with (S)-valinol proceeds under kinetic control to give a major product, (4bR,7S,aS)-6,7-dihydro-7-isopropyldibenz[c,e]oxazolo[3,2-a]azepin-9(4bH)-one 6a (84%), in which the biaryl axis has the (S)-configuration. Heating 6a at 140°C with a catalytic amount of acid gives rise to an equilibrium dominated by the diastereoisomeric (4bS,7S)-lactam 6b (6a:6b ratio 27:73), in which the biaryl unit has the (R)-configuration. The structures of both lactams were established by X-ray crystallography; no other diastereoisomers were obtained. 相似文献
60.
In this paper, we obtain considerable spin-orbit (SO) parameters in AlxGa1-xN/GaN quantum wells (QWs) with sheet carrier concentration Ns=120×1011/cm2 . With increasing Al content (x) of the barrier, the SO parameters increase as a whole, and the two major contributions are found to be the decrease of the expansion region of the envelope functions and the increase of the polarized electric field in the well. Compared with the Rashba parameters for the first two subbands, the intersubband SO parameter is a bit smaller and varies more slowly with x. The results indicate the SO parameters, especially the Rashba parameters can be engineered by the Al composition of the barrier, which may be helpful to the spin manipulation of III-nitride low-dimensional heterostructures. 相似文献