全文获取类型
收费全文 | 3690篇 |
免费 | 142篇 |
国内免费 | 5篇 |
专业分类
化学 | 2025篇 |
晶体学 | 16篇 |
力学 | 65篇 |
数学 | 485篇 |
物理学 | 1246篇 |
出版年
2022年 | 32篇 |
2021年 | 39篇 |
2020年 | 47篇 |
2019年 | 40篇 |
2018年 | 42篇 |
2017年 | 35篇 |
2016年 | 117篇 |
2015年 | 87篇 |
2014年 | 113篇 |
2013年 | 177篇 |
2012年 | 176篇 |
2011年 | 213篇 |
2010年 | 120篇 |
2009年 | 114篇 |
2008年 | 169篇 |
2007年 | 180篇 |
2006年 | 172篇 |
2005年 | 138篇 |
2004年 | 136篇 |
2003年 | 103篇 |
2002年 | 66篇 |
2001年 | 79篇 |
2000年 | 66篇 |
1999年 | 65篇 |
1998年 | 56篇 |
1997年 | 38篇 |
1996年 | 50篇 |
1995年 | 46篇 |
1994年 | 50篇 |
1993年 | 53篇 |
1992年 | 45篇 |
1991年 | 46篇 |
1990年 | 44篇 |
1989年 | 40篇 |
1988年 | 39篇 |
1987年 | 35篇 |
1986年 | 29篇 |
1985年 | 46篇 |
1984年 | 49篇 |
1983年 | 34篇 |
1982年 | 42篇 |
1981年 | 38篇 |
1980年 | 41篇 |
1979年 | 30篇 |
1978年 | 33篇 |
1977年 | 33篇 |
1976年 | 31篇 |
1975年 | 29篇 |
1974年 | 27篇 |
1973年 | 25篇 |
排序方式: 共有3837条查询结果,搜索用时 15 毫秒
971.
Vibrational corrections (zero-point and temperature dependent) of the H-D spin-spin coupling constant J(HD) for six transition metal hydride and dihydrogen complexes have been computed from a vibrational average of J(HD) as a function of temperature. Effective (vibrationally averaged) H-D distances have also been determined. The very strong temperature dependence of J(HD) for one of the complexes, [Ir(dmpm)Cp*H2]2 + (dmpm = bis(dimethylphosphino)methane) can be modeled simply by the Boltzmann average of the zero-point vibrationally averaged JHD of two isomers. For this complex and four others, the vibrational corrections to JHD are shown to be highly significant and lead to improved agreement between theory and experiment in most cases. The zero-point vibrational correction is important for all complexes. Depending on the shape of the potential energy and J-coupling surfaces, for some of the complexes higher vibrationally excited states can also contribute to the vibrational corrections at temperatures above 0 K and lead to a temperature dependence. We identify different classes of complexes where a significant temperature dependence of J(HD) may or may not occur for different reasons. A method is outlined by which the temperature dependence of the HD spin-spin coupling constant can be determined with standard quantum chemistry software. Comparisons are made with experimental data and previously calculated values where applicable. We also discuss an example where a low-order expansion around the minimum of a complicated potential energy surface appears not to be sufficient for reproducing the experimentally observed temperature dependence. 相似文献
972.
Král V Lang K Králová J Dvorák M Martásek P Chin AO Andrievsky A Lynch V Sessler JL 《Journal of the American Chemical Society》2006,128(2):432-437
Enhanced hydrolysis rates for the cleavage of bis(4-nitrophenyl)phosphate (BNPP), a model phosphodiester, may be achieved by using appropriately designed ditopic receptors containing the known phosphate-binding nucleus, sapphyrin, attached covalently to suitably oriented polyhydroxyl subunits. Evidence for the interaction between sapphyrin and BNPP comes from solid-state X-ray diffraction analysis of a diprotonated dihydroxylated sapphyrin-BNPP complex and from solution-phase (31)P NMR spectroscopic binding studies. The sapphyrins described in this paper may have a role to play as oligonucleotide cleavage agents. 相似文献
973.
Ulrich A Adonin A Jacoby J Turtikov V Fernengel D Fertman A Golubev A Hoffmann DH Hug A Krücken R Kulish M Menzel J Morozov A Ni P Nikolaev DN Shilkin NS Ternovoi VY Udrea S Varentsov D Wieser J 《Physical review letters》2006,97(15):153901
High-energy heavy ions are an ideal tool to generate homogeneously excited, extended volumes of nonthermal plasmas. Here, the high-energy loss (dE/dx) and absolute power deposition of heavy ions interacting with matter has been used to pump an ultraviolet laser. A pulsed 70 MeV/u 238U beam with up to 2.5 x 10(9) particles in approximately 100 ns beam bunches was stopped in a 1.2 m long laser cell filled with a 1.6 bar Ar-Kr-F2 mixture (typically 50%:49.9%:0.1%). Laser effect on the 248 nm KrF* excimer transition is clearly demonstrated. 相似文献
974.
Jakubowski MW Schmitz O Abdullaev SS Brezinsek S Finken KH Krämer-Flecken A Lehnen M Samm U Spatschek KH Unterberg B Wolf RC;TEXTOR Team 《Physical review letters》2006,96(3):035004
The magnetic-field perturbation produced by the dynamic ergodic divertor in TEXTOR changes the topology of the magnetic field in the plasma edge, creating an open chaotic system. The perturbation spectrum contains only a few dominant harmonics and therefore it can be described by an analytical model. The modeling is performed in the vacuum approximation without assuming a backreaction of the plasma and does not rely on any experimentally obtained parameters. It is shown that this vacuum approximation predicts in many details the experimentally observed plasma structure. Several experiments have been performed to prove that the plasma edge behavior is defined mostly by the magnetic topology of the perturbed volume. The change in the transport can be explained with the knowledge of only the magnetic structures; i.e., the ergodic pattern dominates the plasma properties. 相似文献
975.
976.
We give an introduction to basic harmonic analysis and representation theory for homogeneous spaces Z = G/H attached to a real reductive Lie group G. A special emphasis is made to the case where Z is real spherical. 相似文献
977.
Jochen Niemeyer 《Journal of organometallic chemistry》2010,695(14):1801-2052
Condensation of the O-protected hydroxyferrocene carbaldehyde (Sp)-1 with suitable diamines, followed by liberation of the hydroxyferrocene moiety leads to a new type of ferrocene-based salen ligands (3). While the use of ethylenediamine in the condensation reaction yields the planar-chiral ethylene-bridged ligand [(Sp,Sp)-3a], reaction with the enantiomers of trans-1,2-cyclohexylendiamine gives rise to the corresponding diastereomeric cyclohexylene-bridged systems [(S,S,Sp,Sp)-3b and (R,R,Sp,Sp)-3c], which feature a combination of a planar-chiral ferrocene unit with a centrochiral diamine backbone. Starting with the ferrocene-aldehyde derivative (Rp)-1, the enantiomeric ligand series (3d/e/f) is accessible via the same synthetic route.The (Sp)-series of these newly developed N2O2-type ligands was used for the construction of the corresponding mononuclear bis(isopropoxy)titanium (4a/b/c), methylaluminum (5a/b/c) and chloroaluminum-complexes (6a/b/c), which were isolated in good yields and identified by X-ray diffraction in several cases. The aluminum complexes (5/6) were successfully used in the Lewis-acid catalyzed addition of trimethylsilylcyanide to benzaldehyde, yielding the corresponding cyanohydrins in 45-62% enantiomeric excess. 相似文献
978.
Meso‐substituted A4‐porphyrins bearing 3,4,5‐trialkoxyphenyl substituents are efficiently synthesized and characterized. Porphyrins bearing twelve C10 and C11 alkyl chains turned out to be liquid at room temperature. The remaining porphyrins, bearing C8, C9, C12, and C18 alkyl chains, have low melting points and high solubility in nonpolar solvents. Their differential scanning calorimetry distinctly shows, in most cases, only one phase transition. 相似文献
979.
Tipmanee V Oberhofer H Park M Kim KS Blumberger J 《Journal of the American Chemical Society》2010,132(47):17032-17040
The acceleration of electron transfer (ET) rates in redox proteins relative to aqueous solutes can be attributed to the protein's ability to reduce the nuclear response or reorganization upon ET, while maintaining sufficiently high electronic coupling. Quantitative predictions of reorganization free energy remain a challenge, both experimentally and computationally. Using density functional calculations and molecular dynamics simulation with an electronically polarizable force field, we report reorganization free energies for intraprotein ET in four heme-containing ET proteins that differ in their protein fold, hydrophilicity, and solvent accessibility of the electron-accepting group. The reorganization free energies for ET from the heme cofactors of cytochrome c and b(5) to solvent exposed Ru-complexes docked to histidine residues at the surface of these proteins fall within a narrow range of 1.2-1.3 eV. Reorganization free energy is significantly lowered in a designed 4-helix bundle protein where both redox active cofactors are protected from the solvent. For all ET reactions investigated, the major components of reorganization are the solvent and the protein, with the solvent contributing close to or more than 50% of the total. In three out of four proteins, the protein reorganization free energy can be viewed as a collective effect including many residues, each of which contributing a small fraction. These results have important implications for the design of artificial electron transport proteins. They suggest that reorganization free energy may in general not be effectively controlled by single point mutations, but to a large extent by the degree of solvent exposure of the ionizable cofactors. 相似文献
980.
St Petkov P Vayssilov GN Krüger S Rösch N 《Physical chemistry chemical physics : PCCP》2006,8(11):1282-1291
Using a gradient-corrected density functional method, we studied computationally how single impurity atoms affect the structure and the properties of a Ni4 cluster. H and O atoms coordinate at a Ni-Ni bond, inducing small changes to the structure of bare Ni4 which is essentially a tetrahedron. For a C impurity, we found three stable structures at a Ni4 cluster. In the most stable geometry, the carbon atom cleaves a Ni-Ni bond of Ni4, binding to all Ni atoms. Inclusion of the impurity atom leads to a partial oxidation of the metal atoms and, in the most stable structures, reduces the spin polarization of the cluster compared to bare Ni4. An H impurity interacts mainly with the Ni 4s orbitals, whereas the Ni 3d orbitals participate strongly in the bonding with O and C impurity atoms. For these impurity atoms, Ni 3d contributions dominate the character of the HOMO of the ligated cluster, in contrast to the HOMO of bare Ni4 where Ni 4s orbitals prevail. We also discuss a simple model which relates the effect of a H impurity on the magnetic state of metal clusters to the spin character (minority or majority) of the LUMO or HOMO of the bare metal cluster. 相似文献