全文获取类型
收费全文 | 682篇 |
免费 | 17篇 |
国内免费 | 2篇 |
专业分类
化学 | 496篇 |
晶体学 | 4篇 |
力学 | 17篇 |
数学 | 37篇 |
物理学 | 147篇 |
出版年
2021年 | 6篇 |
2020年 | 3篇 |
2018年 | 5篇 |
2016年 | 8篇 |
2015年 | 12篇 |
2014年 | 9篇 |
2013年 | 13篇 |
2012年 | 21篇 |
2011年 | 52篇 |
2010年 | 29篇 |
2009年 | 18篇 |
2008年 | 39篇 |
2007年 | 33篇 |
2006年 | 40篇 |
2005年 | 58篇 |
2004年 | 34篇 |
2003年 | 15篇 |
2002年 | 17篇 |
2001年 | 10篇 |
2000年 | 13篇 |
1999年 | 7篇 |
1998年 | 10篇 |
1997年 | 11篇 |
1996年 | 16篇 |
1995年 | 5篇 |
1994年 | 6篇 |
1993年 | 10篇 |
1992年 | 6篇 |
1991年 | 5篇 |
1990年 | 12篇 |
1989年 | 9篇 |
1988年 | 11篇 |
1987年 | 12篇 |
1986年 | 11篇 |
1985年 | 11篇 |
1984年 | 4篇 |
1983年 | 5篇 |
1982年 | 3篇 |
1981年 | 13篇 |
1980年 | 6篇 |
1979年 | 12篇 |
1978年 | 21篇 |
1977年 | 15篇 |
1976年 | 9篇 |
1975年 | 7篇 |
1974年 | 8篇 |
1973年 | 4篇 |
1972年 | 3篇 |
1971年 | 3篇 |
1969年 | 3篇 |
排序方式: 共有701条查询结果,搜索用时 0 毫秒
51.
Dean M. Philipp William A. Goddard Michael J. Mullins Phillip S. Athey 《Tetrahedron letters》2004,45(28):5441-5444
We have been engaged in a search for coordination catalysts for the copolymerization of polar monomers (such as vinyl chloride and vinyl acetate) with ethylene. We have been investigating complexes of late transition metals with heterocyclic ligands. In this report we describe the synthesis of a symmetrical bis-thiadiazole. We have characterized one of the intermediates using single crystal X-ray diffraction. Several unsuccessful approaches toward 1 are also described, which shed light on some of the unique chemistry of thiadiazoles. 相似文献
52.
P. Goddard W. Nahm D. Olive A. Schwimmer 《Communications in Mathematical Physics》1986,107(2):179-212
A vertex operator construction is given for the level one representations of the affine Kac-Moody algebras associated with non-simply-laced finite-dimensional Lie algebras, using free boson and interacting fermion fields. The fermion fields are constructed explicitly and a detailed discussion is given of the theory of the cocycles necessary for this and other vertex operator constructions. The construction is related in detail to the folding of Dynkin diagrams and a generalisation of it yields Freudenthal's magic square.On leave from the Weizmann Institute, Israel 相似文献
53.
E. Bonvin R. Bopp L. J. Carroll A. J. Cass S. U. Chung M. Donnat P. A. Dorsaz M. E. Feliks L. Fluri J. N. Jackson M. N. Kienzle-Focacci J. G. Lynch M. Martin L. Mathys P. J. Negus L. Perini R. Poultney W. H. Range L. Rosselet S. W. Snow A. S. Thompson R. M. Turnbull M. Werlen WA -Collaboration 《Zeitschrift fur Physik C Particles and Fields》1989,41(4):591-598
A search for pairs of highp T prompt photons produced in hydrogen by a 280 GeV/c incidentπ - beam has been carried out using a fine-grained electromagnetic calorimeter and the Omega spectrometer at the CERN SPS. Clear evidence for the existence of such events is found with a six standard deviation signal forp T >3.0 GeV/c. The cross-sections are consistent with beyond leading order QCD calculations. A discussion on the determination of α s is also presented. 相似文献
54.
Gupta R Baldock SJ Carreras P Fielden PR Goddard NJ Mohr S Razavi BS Brown BJ 《Lab on a chip》2011,11(23):4052-4056
The primary requirement for a mixing operation in droplet-based microfluidic devices is an accurate pairing of droplets of reaction fluids over an extended period of time. In this paper, a novel device for self-synchronous production of droplets has been demonstrated. The device uses a change in impedance across a pair of electrodes introduced due to the passage of a pre-formed droplet to generate a second droplet at a second pair of electrodes. The device was characterised using image analysis. Droplets with a volume of ~23.5 ± 3.1 nl (i.e.~93% of the volume of pre-formed droplets) were produced on applying a voltage of 500 V. The synchronisation efficiency of the device was 83%. As the device enables self-synchronised production of droplets, it has a potential to increase the reliability and robustness of mixing operations in droplet-based microfluidic devices. 相似文献
55.
Vincent S. Smentkowski John T. Yates Jr. Xiaojie Chen William A. Goddard III 《Surface science》1997,370(2-3):209-231
The radiation-induced decomposition of C4F9I and CF3I overlayers at 119 K on diamond (100) surfaces has been shown to be an efficient route to fluorination of the diamond surface. X-ray photoelectron spectroscopy has been used for photoactivation as well as for studying the photodecomposition of the fluoroalkyl iodide molecules, the attachment of the photofragments to the diamond surface, and the thermal decomposition of the fluoroalkyl ligands. Measured chemical shifts agree well with ab initio calculations of both C 1s and F 1s binding energies. It is found that chemisorbed CF3 groups on diamond (100) decompose by 300 K whereas C4F9 groups decompose over the range 300 to 700 K and this reactivity difference is rationalized on steric grounds. Both of these thermal decomposition processes produce surface C---F bonds on the diamond. The surface C---F species thermally decompose over a wide temperature range extending up to 1500 K. Hydrogen passivation of the diamond surface is ineffective in preventing free radical attack from the photodissociated products of the fluoroalkyl iodides; I atoms produced photolytically abstract H from surface C---H bonds to yield hydrogen iodide at 119 K allowing diamond fluorination. The attachment of chemisorbed F species to the diamond (100) surface causes band bending as the surface states are occupied as a result of chemisorption. This results in a shift to higher binding energy of the diamond-related C 1s levels present in the surface and subsurface regions which are sampled by XPS on the diamond. The use of photoactivation of fluoroalkyl iodides for the fluorination of diamond surfaces provides a convenient route compared to other methods involving the action of atomic F, molecular F2, XeF2 and F-containing plasmas. 相似文献
56.
Dr. Rüdiger W. Seidel Richard Goddard Constantin Hoch Iris M. Oppel 《无机化学与普通化学杂志》2011,637(11):1545-1554
Attempts to crystal engineer metallosupramolecularcomplexes from Cu(phen)2+ building blocks and the prototypical,rod‐like, exo‐bidentate ligand 4,4′‐bipyridine (4,4′‐bipy) by layering techniques are described. Reactions of Cu(phen)2+ (phen = 1,10‐phenanthroline) with 4,4′‐bipy in the presence of NO3– counterions yielded two distinct, discrete, dinuclear, Ci symmetric, dumbbell‐typecomplexes, [{Cu(NO3)2(phen)}2(4,4′‐bipy)] ( 1 ) and [{Cu(NO3)(phen)(H2O)}2(4,4′‐bipy)](NO3)2 ( 2 ), depending upon the mixture of solvents used for crystallization. In compound 1 , a mono‐ and a bidentate nitrato group coordinate to Cu2+, whereas in 2 the monodentate nitrato groups are replaced by aqua ligands, which introduce additional hydrogen‐bond donor functionality to the molecule. The crystal structure of 1 was determined by single‐crystal X‐ray analysis at 296 and 110 K. Upon cooling, a disorder‐order transition occurs, with retention of the space group symmetry. The crystal structure of 2 at room temperature was reported previously [Z.‐X. Du, J.‐X. Li, Acta Cryst. 2007 , E63, m2282]. We have redetermined the crystal structure of 2 at 100 K. A phase transition is not observed for 2 , but the low temperature single‐crystal structure determination is of significantly higher precision than the room temperature study. Both 1 and 2 are obtained phase‐pure, as proven by powder X‐ray diffraction of the bulk materials. Crystals of [Cu(phen)(CF3SO3)2(4,4′‐bipy) · 0.5H2O]n ( 3 ), a one‐dimensional coordination polymer, were obtained from [Cu(CF3SO3)2(phen)(H2O)2] and 4,4′‐bipy. In 3 , Cu(phen)2+ corner units are joined by 4,4′‐bipy via the two vacant cis sites to form polymeric zig‐zag chains, which are tightly packed in the crystal. Compounds 1 – 3 were further studied by infrared spectroscopy. 相似文献
57.
The effect of a remote substituent on regioselectivity in the oxymercuration of 2-substituted norbornenes has been investigated experimentally and theoretically using density functional theory (DFT). Regioselectivities of 1:1 to 14:1 were observed with various 2-substituted norbornenes. Exo-2-substituted norbornenes always gave greater regioselectivities compared to the corresponding endo-2-substituted norbornenes. The effects of solvents on the regioselectivity have also been examined, and ethereal solvents were found to be the best choice giving the optimal yield and regioselectivity. The relative rate of oxymercuration was estimated by competition experiments. The least reactive substrate (X = OAc) gave the highest regioselectivity. According to DFT predictions, the increased difference between the reaction barriers that results in the greater regioselectivity is correlated directly with the larger polarity of the C=C double bond, which is attacked by the mercury and oxygen. A number of stable exo and endo conformers were predicted. All exo conformers show the same polarity of the double bond, while some endo conformers have a reversal of this polarity. All the conformers except those with the OAc substituent are very close in energy and thus should react. The existence of a mixture of endo conformers with the C=C double bond of opposite polarity clearly explains a decrease in regioselectivity for the endo species. The origin of the greatest regioselectivity for the OAc-2-norbornenes lies in the fact that the conformer with the largest polarity is notably lower in energy than others due to an internal C-H-O hydrogen bond. 相似文献
58.
The First Crystal Structure of a Reactive Dirhodium Carbene Complex and a Versatile Method for the Preparation of Gold Carbenes by Rhodium‐to‐Gold Transmetalation 下载免费PDF全文
Dr. Christophe Werlé Dr. Richard Goddard Prof. Alois Fürstner 《Angewandte Chemie (International ed. in English)》2015,54(51):15452-15456
The dirhodium carbene derived from bis(4‐methoxyphenyl)diazomethane and [Rh(tpa)4]?CH2Cl2 (tpa=triphenylacetate) was characterized by UV, IR, and NMR spectroscopy, HRMS, as well as by X‐ray diffraction. The isolated complex exhibits prototypical rhodium carbene reactivity in that it cyclopropanates 4‐methoxystyrene at low temperature. Experimental structural information on this important type of reactive intermediate is extremely scarce and thus serves as a reference point for mechanistic discussions of rhodium catalysis in general. Moreover, dirhodium carbenes are shown to undergo remarkably facile carbene transfer on treatment with [LAuNTf2] (L=phosphine). This formal transmetalation opens a valuable new entry into gold carbene complexes that cannot easily be made otherwise; three fully characterized representatives illustrate this aspect. 相似文献
59.
Adsorption-desorption properties and surface structural chemistry of chlorine on Cu(111) and Ag(111)
The adsorption, desorption, and structural properties of chlorine adlayers on Cu(111) and Ag(111) have been studied by LEED, Auger, Δ?, and thermal desorption measurements. Ancillary experiments were also carried out on cuprous chloride for purposes of comparison with the Cu(111)-Cl data. Chlorine adsorption is rapid on both metals and follows precursor kinetics, the absolute initial sticking probabilities being ~1.0 (Cu) and ~0.5 (Ag). Δ? results suggest that significant depolarisation of the chemisorption bond occurs at high coverages, the maximum values being + 1.2 eV (Cu) and + 1.8 eV (Ag). On Cu(111), adsorption leads to the formation of a sequence of well-ordered phases; in order of increasing coverage, these are as follows: (√3 × √3)R30°, (12√3 × 12√3)R30°, (4√7 × 4√7)R19.2°, and (6√3 × 6√3)R30°. On Ag(111) (√3 × √3)R30°, and (10 × 10) structures are observed. All six structures are susceptible to a straightforward interpretation in terms of coincidence lattices resulting from the progressive uniform compression of a hexagonal layer of Cl atoms. This interpretation is consistent with all the experimental results, and gives values for the nearest-neighbour ClCl spacing on both Cu(111) and Ag(111) which are in good agreement with other work on other surfaces. Chlorine desorbs exclusively as atoms from both metals with first-order desorption kinetics, and apparent desorption energies of 236 (Cu) and 209 (Ag) kJ mol?1. These values, which depend on an assumed pre-exponential factor of 1013 s?1, are shown to be inconsistent with the thermochemical constraints on the system necessitated by the complete absence of Cl2 desorption. Lower limits for the pre-exponential factors are then deduced, and the values are found to be consistent with the differences between the CuCl and AgCl systems. 相似文献
60.
Baum A Scully PJ Basanta M Thomas CL Fielden PR Goddard NJ Perrie W Chalker PR 《Optics letters》2007,32(2):190-192
Femtosecond, subablation threshold photomodification of poly(methyl methacrylate) (PMMA) at 387 nm is explored to enable fabrication of optical components. Volatile fragment analysis (thermal desorption gas chromatography-mass spectrometry) and molecular weight distribution monitoring (size exclusion chromatography) suggest photochemical modification, involving direct cleavage of the polymer backbone and propagation via chain unzipping under formation of monomers, similar to the pyrolytic degradation of PMMA. Waveguides were produced in undoped, clinical-grade PMMA, showing an increased refractive index in the laser focal region (Dnmax=4x10(-3)). 相似文献