全文获取类型
收费全文 | 2035篇 |
免费 | 41篇 |
国内免费 | 387篇 |
专业分类
化学 | 2023篇 |
晶体学 | 22篇 |
力学 | 17篇 |
综合类 | 4篇 |
数学 | 3篇 |
物理学 | 394篇 |
出版年
2024年 | 7篇 |
2023年 | 83篇 |
2022年 | 29篇 |
2021年 | 62篇 |
2020年 | 46篇 |
2019年 | 68篇 |
2018年 | 42篇 |
2017年 | 56篇 |
2016年 | 59篇 |
2015年 | 55篇 |
2014年 | 91篇 |
2013年 | 134篇 |
2012年 | 109篇 |
2011年 | 142篇 |
2010年 | 73篇 |
2009年 | 97篇 |
2008年 | 118篇 |
2007年 | 130篇 |
2006年 | 149篇 |
2005年 | 91篇 |
2004年 | 126篇 |
2003年 | 99篇 |
2002年 | 73篇 |
2001年 | 69篇 |
2000年 | 51篇 |
1999年 | 56篇 |
1998年 | 74篇 |
1997年 | 54篇 |
1996年 | 37篇 |
1995年 | 29篇 |
1994年 | 26篇 |
1993年 | 28篇 |
1992年 | 13篇 |
1991年 | 18篇 |
1990年 | 9篇 |
1989年 | 6篇 |
1988年 | 15篇 |
1987年 | 6篇 |
1986年 | 3篇 |
1985年 | 3篇 |
1982年 | 2篇 |
1981年 | 5篇 |
1980年 | 5篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1977年 | 3篇 |
1975年 | 2篇 |
1974年 | 2篇 |
1968年 | 1篇 |
1967年 | 1篇 |
排序方式: 共有2463条查询结果,搜索用时 31 毫秒
91.
The X-ray crystal structures of a series of lithium quinolates – lithium 8-hydroxyquinolinate (Liq), lithium 2-methyl-8-hydroxyquinolinate (MeLiq), and 2-phenyl-8-hydroxquinolinate (PhLiq), are compared. The substitution at the 2-position of the 8-hydroxyquinoline ligand has significant impact on the aggregation of the lithium complex in the crystalline state. Liq and MeLiq molecules crystallize as hexamers, whereas PhLiq crystallizes as a tetramer. The possible influence of crystal-packing forces on the preferred cluster structure was probed using density functional theory calculations on a systematically varied set of Liq, MeLiq, and PhLiq clusters. For Liq and MeLiq, the observed structures match the most stable computed structures. In the PhLiq case, the observed tetrameric structure is computed to be less stable (+1.2 kcal/mol/monomer) than the lowest energy structure, a hexamer. In this case, solid-state effects probably outweigh small differences in cluster stability. 相似文献
92.
The new [Li(DME)3+] salt of the previously-known tetra(tert-butyl)erbate(III) anion [Er(t-Bu)4−] has been prepared and structurally characterized. The erbium(III) center is ligated by four tert-butyl groups in an approximately tetrahedral arrangement. The C–Er–C angles between the tert-butyl groups range from 108.8(3)° to 111.2(3)° and the Er–C distances range from 2.352(6) to 2.395(6) Å. The lithium cation is surrounded by three DME molecules, which form a distorted octahedral coordination sphere. Attempts to oxidize the analogous terbate complex [Li(DME)3][Tb(t-Bu)4] and its cerium analog to electrically neutral tetra(alkyl)lanthanide(IV) compounds are described. 相似文献
93.
Syntheses and Structures of Trilithium Cyclotriphosphazenates Equipped with 2‐Halo‐aryl Substituents
Hexakis (2‐halo‐anilino) cyclotriphosphazenes (2‐X‐C6H4NH)6P3N3 {X = F ( 1d ), Cl ( 1e ), Br ( 1f )} were prepared by refluxing mixtures of hexachloro cyclotriphosphazene, 2‐haloaniline and triethylamine in toluene and characterized by single crystal X‐ray diffraction. 1d , 1e and 1f were reacted with nBuLi in thf. Reactions were monitored with 31P NMR. Addition of three equivalents of nBuLi yields lithium complexes of trianionic phosphazenates [{(thf)2Li}3{(2‐X‐C6H4N)3(2‐X‐C6H4NH)3P3N3}] {X= F ( 2d ), Cl ( 2e ) and Br ( 2f )}. 2d , 2e and 2f were structurally characterized by X‐ray diffraction, which reveals monomeric cis‐metalated phosphazenates featuring central P3N3 ring systems of chair conformation. Lithium ions reside in three N(eq)‐P‐N(endo) chelation sites at one face of the P3N3 ring system. Li…X distances are rather long (> 3Å) indicating no Li‐X interactions. 相似文献
94.
Crystalline [Y(OH2)3(NCMe)(benzo-15-crown-5)][ClO4]3·benzo-15-crown-5-CH3CN can be obtained by slowly cooling a reaction mixture of Y(ClO4)3·n H2O with benzo-15-crown-5 in a solution of acetonitrile and methanol (3 : 1) from 60°C to room temperature. The crystal structure of this complex has been determined at –150 and 20°C. The complex is triclinic,P
. At –150°C the cell parameters area = 11.986(4),b = 12.071(7),c = 16.364(5) Å, = 93.56(3), = 98.68(3), = 109.68(4)°, vol = 2187 Å3, andD
calc = 1.61 g cm–3 forZ = 2 formula units. 3633 independently observed [F
o 5(F
o)] reflections were used in the final least-squares refinement leading to an agreement index ofR = 0.048. The Y(III) ion coordination geometry approximates a tricapped trigonal prism with three water molecules and three benzo-15-crown-5 oxygen atoms forming the prism, with the two remaining benzo-15-crown-5 oxygen atoms and the acetonitrile molecule completing the coordination as capping atoms. The three water molecules hydrogen bond a second crown ether molecule and two of the perchlorate anions. The two acetonitrile molecules have contacts with perchlorate oxygen atoms close enough for some weak interaction. One perchlorate is ordered, one is partially disordered as is the coordinated solvent molecule, and the third anion is totally disordered. The two unique crown ether molecules have distinctively different conformations.For Part 20, see reference [1]. 相似文献
95.
Hüseyin Göktepe 《中国化学会会志》2013,60(2):218-222
Dy doping and carbon coating are adopted to synthesize a LiFePO4 cathode material in a simple solution environment. The samples were characterized by X‐ray diffraction (XRD) and scanning electron microscopy (SEM). Their electrochemical properties were investigated by cyclic voltammetry (CV) and galvanostatic charge‐discharge tests. An initial discharge capacity of 153 mAh/g was achieved for the LiDy0.02Fe0.98PO4/C composite cathode with a rate of 0.1 C. In addition the electronic conductivity of Dy doped LiFePO4/C was enhanced to 1.9 × 10?2 Scm?1. The results suggest that the improvement of the electrochemical properties are attributed to the dysprosium doping and carbon coating which facilitates the phase transformation between triphylite and heterosite during cycling. XRD data indicate that doping did not destroy the lattice structure of LiFePO4. To evaluate the effect of Dy substitution, cyclic voltammetry was used at room temperature. prepared. From Cv measurement a more symmetric curve with smaller interval between the cathodic and anodic peak current was obtained by Dy substitution. This denoted a decreasing of polarization with Dy substitution, which illustrated an enhancement of electrochemical performances. 相似文献
96.
Nahar Singh Rama Devi Ramachandran Ajit Kumar Sarkar 《International journal of environmental analytical chemistry》2013,93(10):891-896
Silica is removed from fly ash sample by hydroflourination for its effective determination gravimetrically and the remaining residue is subjected to lithium tetraborate (Li2B4O7) fusion followed by dissolution in dilute nitric acid to obtain a clear solution in which elements including aluminum (Al), iron (Fe), calcium (Ca), magnesium (Mg), sodium (Na), potassium (K), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), nickel (Ni), copper (Cu) and zinc (Zn), have been determined by Flame Atomic Absorption Spectrometry (FAAS). Two fly ash samples analyzed by the proposed method have been received from the National Council of Cement and Building Materials (NCCBM), India (proposed CRM in future) and fly ash CRM 1633 (b) from NIST, USA. The validity of the method has been established by analyzing fly ash CRM 1633 (b) as reference standard. The standard deviation has been calculated for each measurement. 相似文献
97.
R. M. Montereali 《辐射效应与固体损伤》2013,168(6-12):545-551
Research activities concerned with color centers in alkali halide films started recently. The use of versatile, well-assessed, and low-cost fabrication techniques consisting of physical vapor deposition of Lithium Fluoride (LiF) films combined with direct writing lithographic processes allows the realization of miniaturized structures, like broad-band emitters, channel waveguides, optical microcavities and point-light sources emitting in the visible spectral range. Promising results have been obtained in the generation, amplification and waveguiding of visible light in LiF treated by low energy electron beams, where the efficient formation of stable primary and aggregate color centers also induces a local modification of the refractive index. A brief overview of the investigated optical properties is presented together with a short discussion about their perspectives of applications in optoelectronics. 相似文献
98.
99.
100.
In the paper results of the investigation of the influence of electric properties of the environment surrounding LiNbO3 crystals on photorefractive effect induced in these crystals by Gaussian Ar+ laser beam with various intensities are presented. We show spatial and temporal dependences of changes of the refractive index obtained experimentally in LiNbO3: Fe and LiNbO3: Fe:Mn samples surrounded by media with different electric conductivities and different permittivities (water, air, water solution of CaCl2). The space and time dependences of the refractive index changes induced by the Ar+ laser beam are observed by means of the Mach–Zehnder interferometer using light from HeNe laser. The experimentally obtained results are in a good agreement with those following from numerical calculations using the manifold mirroring method. The agreement between calculated and experimental results indicates that the polarization charge at the photorefractive crystal/surrounding medium boundary significantly influences the photorefractive process in the crystal. The experimentally observed slow spontaneous decrease of the refractive index change in a sample placed into a slightly conducting medium (air) after switching off the beam also indicates that the polarization charge in the sample's surroundings affects the photorefraction. 相似文献