全文获取类型
收费全文 | 4146篇 |
免费 | 252篇 |
国内免费 | 21篇 |
专业分类
化学 | 3198篇 |
晶体学 | 16篇 |
力学 | 80篇 |
数学 | 536篇 |
物理学 | 589篇 |
出版年
2023年 | 52篇 |
2022年 | 73篇 |
2021年 | 84篇 |
2020年 | 135篇 |
2019年 | 109篇 |
2018年 | 63篇 |
2017年 | 79篇 |
2016年 | 174篇 |
2015年 | 150篇 |
2014年 | 175篇 |
2013年 | 199篇 |
2012年 | 305篇 |
2011年 | 257篇 |
2010年 | 149篇 |
2009年 | 141篇 |
2008年 | 227篇 |
2007年 | 215篇 |
2006年 | 188篇 |
2005年 | 196篇 |
2004年 | 183篇 |
2003年 | 121篇 |
2002年 | 154篇 |
2001年 | 66篇 |
2000年 | 60篇 |
1999年 | 51篇 |
1998年 | 58篇 |
1997年 | 50篇 |
1996年 | 54篇 |
1995年 | 38篇 |
1994年 | 32篇 |
1993年 | 31篇 |
1992年 | 42篇 |
1991年 | 24篇 |
1990年 | 27篇 |
1989年 | 33篇 |
1988年 | 33篇 |
1987年 | 31篇 |
1986年 | 23篇 |
1985年 | 27篇 |
1984年 | 31篇 |
1983年 | 26篇 |
1982年 | 21篇 |
1981年 | 38篇 |
1980年 | 24篇 |
1979年 | 21篇 |
1978年 | 17篇 |
1977年 | 27篇 |
1976年 | 10篇 |
1975年 | 12篇 |
1970年 | 13篇 |
排序方式: 共有4419条查询结果,搜索用时 15 毫秒
51.
Sergey P. Verevkin Wei-Hong Peng Hans-Dieter Beckhaus Christoph Rüchardt 《Structural chemistry》1996,7(5-6):397-404
The standard enthalpies of combustion c
H
o of aliphatic diacetates1 and aromatic diacetates2 were measured calorimetrically. The enthalpies of vaporization vap
H
o or sublimation sub
H
o of1 and2 were obtained from the temperature function of the vapor pressure measured in a flow system. From f
H
o(g) of1 and2 new values of group increments for the estimation of standard enthalpies of formation of these classes of compounds were derived. The geminal interaction energy between the geminal acyloxy groups shows no anomeric stabilization.Geminal Substituent Effects, Part 12, for part 11 see Ref. 7. 相似文献
52.
Molecular dynamics simulations show that gold clusters with about 600-3000 atoms crystallize into a Mackay icosahedron upon cooling from the liquid. A detailed surface analysis shows that the facets on the surface of the Mackay icosahedral gold clusters soften but do not premelt below the bulk melting temperature. This softening is found to be due to the increasing mobility of vertex and edge atoms with temperature, which leads to inter-layer and intra-layer diffusion, and a shrinkage of the average facet size, so that the average shape of the cluster is nearly spherical at melting. 相似文献
53.
The crystal structures of molybdocene‐amino acid compounds of the type [Cp2MoIV(κN, κO‐AA)]+Cl—·xH2O with AA = D ‐phenylalaninato (x = 1.5), DL ‐leucinato (x = 2) and DL ‐valinato (x = 1) have been determined (Cp = η5‐C5H5). The compounds feature an almost planar, five‐membered chelate ring of the aminocarboxylate moiety (deprotonated amino acid) with the molybdenum atom. In the phenylalaninato complex π‐stacking between the phenyl rings is found. The complexes were proven kinetically stable at pH < 1 for at least 24 h. 相似文献
54.
Andreas Heimermann Christoph van Wüllen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(61):15148-15158
Spin Hamiltonian parameters of a pentanuclear Os Ni cyanometallate complex are derived from ab initio wave function based calculations, namely valence-type configuration interaction calculations with a complete active space including spin-orbit interaction (CASOCI) in a single-step procedure. While fits of experimental data performed so far could reproduce the data but the resulting parameters were not satisfactory, the parameters derived in the present work reproduce experimental data and at the same time have a reasonable size. The one-centre parameters (local matrices and single-ion zero field splitting tensors) are within an expected range, the anisotropic exchange parameters obtained in this work for an Os−Ni pair are not exceedingly large but determine the low-T part of the experimental χT curve. Exchange interactions (both isotropic and anisotropic) obtained from CASOCI have to be scaled by a factor of 2.5 to obtain agreement with experiment, a known deficiency of such types of calculation. After scaling the parameters, the isotropic Os−Ni exchange coupling constant is cm−1 and the D parameter of the (nearly axial) anisotropic Os−Ni exchange is −1, so anisotropic exchange is larger in absolute size than isotropic exchange. The negative value of the isotropic J (indicating antiferromagnetic coupling) seemingly contradicts the large-temperature behaviour of the temperature dependent susceptibility curve, but this is caused by the negative g value of the Os centres. This negative g value is a universal feature of a pseudo-octahedral coordination with configuration and strong spin-orbit interaction. Knowing the size of these exchange interactions is important because Os(CN) is a versatile building block for the synthesis of / magnetic materials. 相似文献
55.
From the bulbs of Eucomis punctata L'Hérit. (Liliaceae) and of a hitherto undefined species of Eucomis a new optically active phenolic carboxylic acid, eucomic acid, was isolated. Structure 1 was assigned on the basis of chemical and spectral evidence. The absolute configuration of eucomic acid was determined by its correlation with piscidic acid ((2 R, 3 S)-2-(4′-hydroxybenzyl)-tartaric acid) ( 8 ). Consequently, eucomic acid is (R)-(?)-2-(4′-hydroxybenzyl)-malic acid ( 1 ). For the stereospecific synthesis, methyl cis-p-methoxybenzylidene-succinic acid ( 22 ) was transformed into the γ-lactone 24 which, by catalytic hydrogenolysis, yielded (±)-2-(4′-hydroxybenzyl)-malic acid 1-methyl ester ( 27 ). Resolution with (?)-quinine led to the enantiomeric acids 29 and 30 . The methyl ester of the levorotatory enantiomer 30 was identical with the dimethyl ester 3 of 4′-O-methyl-eucomic acid. 相似文献
56.
Alpha-substituent effects on inversion barriers and NMR chemical shifts have been studied on a set of silyl anions, [X(3-n)Y(n)Si](-) (X, Y=H, CH(3), and SiH(3)). The MP2/6-31+G* optimized structures show a pattern of increasing inversion barriers with augmenting numbers of methyl substituents. The highest barrier of 48.5 kcalmol(-1) is obtained for the (CH(3))(3)Si(-) ion. The silyl group displays the opposite effect by decreasing the inversion barrier to a minimum of 16.3 kcalmol(-1) in (SiH(3))(3)Si(-). The influence of counterions on these barriers is probed by addition of a lithium or potassium cation. In most cases, a decrease of the energy barriers with respect to the bare anions is observed. The (29)Si NMR chemical shifts calculated at the IGLO-DFT and GIAO-MP2 level of theory are also analyzed in view of the substituents and counterions. 相似文献
57.
58.
Grotjahn DB Van S Combs D Lev DA Schneider C Incarvito CD Lam KC Rossi G Rheingold AL Rideout M Meyer C Hernandez G Mejorado L 《Inorganic chemistry》2003,42(10):3347-3355
Inter- and intramolecular hydrogen bonding of an N-H group in pyrazole complexes was studied using ligands with two different groups at pyrazole C-3 and C-5. At C-5, groups such as methyl, i-propyl, phenyl, or tert-butyl were present. At C-3, side chains L-CH(2)- and L-CH(2)CH(2)- (L = thioether or phosphine) ensured formation of chelates to a cis-dichloropalladium(II) fragment through side-chain atom L and the pyrazole nitrogen closest to the side chain. The significance of the ligands is that by placing a ligating side chain on a ring carbon (C-3), rather than on a ring nitrogen, the ring nitrogen not bound to the metal and its attached proton are available for hydrogen bonding. As desired, seven chelate complexes examined by X-ray diffraction all showed intramolecular hydrogen bonding between the pyrazole N-H and a chloride ligand in the cis position. In addition, however, intermolecular hydrogen bonding could be controlled by the substituent at C-5: complexes with either a methyl at C-5 or no substituent there showed significant intermolecular hydrogen bonding interactions, which were completely avoided by placing a tert-butyl group at C-5. The acidity of two complexes in acetonitrile solutions was estimated to be closer to that of pyridinium ion than those of imidazolium or triethylammonium ions. 相似文献
59.
Christoph Meingast Frank Gugenberger Georg Roth Miro Haluška Hans Kuzmany 《Zeitschrift für Physik B Condensed Matter》1994,95(1):67-71
The thermal expansion of vapor-grownC
70 single crystals ahs been investigated using high-resolution capacitance dilatometry from 5–380 K. Measurements were made both parallel and perpendicular to the hexagonalc-axis. Three first-order phase transitions which we associate with the consecutive disordering of theC
70 molecules are observed upon heating at 280 K (long-axis spinning), 300 K (long-axis precession) and 355 K (quasi-free rotation), respectively. The highest-temperature transition exhibits a very large (50 K) thermal hysteresis. Powder and single-crystal X-ray diffraction show that the crystals are predominantly hexagonal-close-packed (HCP) with an idealc/a1.63 above 360 K andc/a1.84 at 295 K. 相似文献
60.
It is shown that a minimal graph with a normal at infinity is in a-priori bounded vertical distance from its approximating halfcatenoid. This is used to show that the exterior contact angle problem is wellposed under natural geometric conditions on the domain, while the exterior Dirichlet problem can be solvable only for data which satisfy an oscillation bound.This paper was written under the support of the Deutsche Forschungsgemeinschaft while the author was visiting the department of mathematics at Stanford University.This article was processed by the author using the LaTEX style filepljour1 from Springer-Verlag. 相似文献