全文获取类型
收费全文 | 6658篇 |
免费 | 298篇 |
国内免费 | 26篇 |
专业分类
化学 | 4796篇 |
晶体学 | 26篇 |
力学 | 105篇 |
数学 | 1037篇 |
物理学 | 1018篇 |
出版年
2023年 | 68篇 |
2022年 | 79篇 |
2021年 | 97篇 |
2020年 | 159篇 |
2019年 | 135篇 |
2018年 | 74篇 |
2017年 | 95篇 |
2016年 | 212篇 |
2015年 | 172篇 |
2014年 | 211篇 |
2013年 | 275篇 |
2012年 | 358篇 |
2011年 | 333篇 |
2010年 | 204篇 |
2009年 | 181篇 |
2008年 | 293篇 |
2007年 | 281篇 |
2006年 | 241篇 |
2005年 | 279篇 |
2004年 | 249篇 |
2003年 | 173篇 |
2002年 | 187篇 |
2001年 | 103篇 |
2000年 | 99篇 |
1999年 | 89篇 |
1998年 | 80篇 |
1997年 | 69篇 |
1996年 | 83篇 |
1995年 | 57篇 |
1994年 | 67篇 |
1993年 | 62篇 |
1992年 | 67篇 |
1991年 | 58篇 |
1990年 | 46篇 |
1989年 | 62篇 |
1988年 | 60篇 |
1987年 | 59篇 |
1986年 | 63篇 |
1985年 | 67篇 |
1984年 | 70篇 |
1983年 | 62篇 |
1982年 | 66篇 |
1981年 | 88篇 |
1980年 | 68篇 |
1979年 | 53篇 |
1978年 | 62篇 |
1977年 | 67篇 |
1976年 | 44篇 |
1971年 | 41篇 |
1970年 | 42篇 |
排序方式: 共有6982条查询结果,搜索用时 78 毫秒
81.
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
82.
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
83.
Helmut Ehrenberg Hermann Pauly Joachim Gröbner 《Journal of solid state chemistry》2004,177(1):227-230
The cubic face-centered structure of LiAl (, at ) transforms into a tetragonal body-centered structure (I41/amd, , at ). This first-order phase transition at about during heating is probably the reason for the so-called “ anomalies” in some physical properties like specific heat, electrical resistivity and nuclear-spin lattice relaxation. This transition seems to be correlated with the composition Li:Al of the alloy and the amount of Li vacancies. 相似文献
84.
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
85.
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
86.
Previously unknown polyfluorocyclohexenyl, and acyclic perfluoroalkenyliodine tetrafluorides were prepared in high yields. Perfluorocyclohex-1-enyliodine tetrafluoride was obtained from pentafluoroiodobenzene using XeF2-NbF5 in aHF. The reaction of C6F5I with the weaker fluorooxidant XeF2-BF3 in 1,1,1,3,3-pentafluorobutane (PFB) yielded C6F5IF2, perfluorocyclohexa-1,4-dienyliodine difluoride, C6F5IF4, perfluorocyclohexa-1,4, and 1,3-dienyliodine tetrafluoride as intermediate products on parallel reaction routes. Both perfluoroalkenyl iodides, cis- and trans-(CF3)2CFCFCFI, reacted with XeF2-BF3 in PFB to give the corresponding perfluoroalkenyliodine tetrafluorides, cis- and trans-(CF3)2CFCFCFIF4. Even perfluoroalkyl iodides can be fluorinated by this reagent as was demonstrated by the preparation of C6F13IF4 from C6F13I. Generally, the CFCIFn fragment (n = 0, 2, or 4) in cyclic or acyclic perfluoroalkenyliodine compounds RFIFn did not undergo a transformation to the corresponding perfluoroalkyliodine compound. Furthermore, no perfluoroorganoiodine hexafluorides were detected in reactions with the fluorooxidant XeF2-aHF or BF3 or NbF5. 相似文献
87.
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
88.
Ohne ZusammenfassungI.H. Schmid undG. Muhr, Ber. dtsch. chem. Ges.70, 421 (1937); II.H. Schmid, Z. Elektrochem.43, 626 (1937); III.H. Schmid, Atti X. Congr. internat. Chim. Roma2, 484 (1938); IV.H. Schmid undA. Woppmann, Mh. Chem.83, 346 (1952); V. und VI.H. Schmid undR. Pfeifer, Mh. Chem.84, 829, 842 (1953); VII.H. Schmid, Mh. Chem.85, 424 (1954); zusammenfassender Ber.:H. Schmid, Chemiker-Ztg.78, 565, 683 (1954); VIII.H. Schmid, Mh. Chem.86, 668 (1955); IX.H. Schmid undA. F. Sami, Mh. Chem.86, 904 (1955); X.H. Schmid undE. Hallaba, Mh. Chem.87, 560 (1956); XI.H. Schmid undA. Woppmann, Mh. Chem.88, 411 (1957);H. Schmid, Mh. Chem.88, 161, 344 (1957); XII.H. Schmid undM. G. Fouad, Mh. Chem.88, 631 (1957);H. Schmid, Österr. Pat. 191 399, Kl. 12e2 (Juni 1957);H. Schmid, Chemiker-Ztg.81, 603 (1957); XIII. und XIV.H. Schmid undCh. Essler, Mh. Chem.88, 1110 (1957);90, 222 (1959); XV.H. Schmid undA. Woppmann, Mh. Chem.90, 903 (1959); XVI.H. Schmid undCh. Essler, Mh. Chem.91, 484 (1960); XVII.H. Schmid undG. Muhr, Mh. Chem.91, 1198 (1960);H. Schmid, Mh. Chem.92, 174 (1961). 相似文献
89.
Scherer LJ Merz L Constable EC Housecroft CE Neuburger M Hermann BA 《Journal of the American Chemical Society》2005,127(11):4033-4041
We describe the synthesis and a novel approach to the conformational analysis of 2,2'-bipyridines (bpy) bearing aromatic rich Frechet-type dendritic wedges of the first and second generation as substituents. The evaporation of solutions of these new ligands on graphite surfaces under ambient conditions results in the formation of self-organized monolayers. Scanning tunneling microscopy (STM) investigations of the monolayers under ambient conditions (air, 298 K) gave images at submolecular and near-atomic resolution. The analysis of the STM images includes the following processes: (i) identification and reproduction of potential homoconformational domains, (ii) exclusion of improper data using quality criteria for drift and feedback artifacts, (iii) compilation of running averages and checking for averaging artifacts, (iv) analysis of three-dimensional and contour plots, (v) calculation of the HOMO properties of the free molecules, and (vi) final conformational assignment based on all accessible information. Following this procedure, two different conformations could be assigned to domains observed in the monolayers of the first-generation (G1) and second-generation (G2) dendritic compounds. Homoconformational domains are observed side-by-side. The different conformations arise from syn or anti arrangements at the ether substituents. An additional conformational effect is found upon treating the G1 domains with HCl gas, when a partial rearrangement of the bpy from trans to cis occurs, concomitant with protonation. 相似文献
90.
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