全文获取类型
收费全文 | 550篇 |
免费 | 31篇 |
国内免费 | 1篇 |
专业分类
化学 | 401篇 |
晶体学 | 6篇 |
力学 | 7篇 |
数学 | 32篇 |
物理学 | 136篇 |
出版年
2023年 | 11篇 |
2022年 | 5篇 |
2021年 | 8篇 |
2020年 | 12篇 |
2019年 | 12篇 |
2018年 | 7篇 |
2017年 | 6篇 |
2016年 | 22篇 |
2015年 | 18篇 |
2014年 | 9篇 |
2013年 | 10篇 |
2012年 | 18篇 |
2011年 | 24篇 |
2010年 | 26篇 |
2009年 | 19篇 |
2008年 | 28篇 |
2007年 | 27篇 |
2006年 | 29篇 |
2005年 | 43篇 |
2004年 | 19篇 |
2003年 | 23篇 |
2002年 | 23篇 |
2001年 | 22篇 |
2000年 | 10篇 |
1999年 | 8篇 |
1998年 | 9篇 |
1997年 | 6篇 |
1996年 | 4篇 |
1995年 | 7篇 |
1994年 | 4篇 |
1993年 | 9篇 |
1992年 | 10篇 |
1991年 | 5篇 |
1990年 | 4篇 |
1988年 | 4篇 |
1987年 | 6篇 |
1985年 | 8篇 |
1984年 | 3篇 |
1983年 | 6篇 |
1982年 | 3篇 |
1980年 | 7篇 |
1979年 | 5篇 |
1978年 | 7篇 |
1975年 | 3篇 |
1971年 | 5篇 |
1968年 | 2篇 |
1961年 | 2篇 |
1920年 | 2篇 |
1896年 | 2篇 |
1887年 | 2篇 |
排序方式: 共有582条查询结果,搜索用时 31 毫秒
11.
12.
Robert F. Kirchner Gilda H. Loew Ulrich T. Mueller-Westerhoff 《Theoretical chemistry accounts》1976,41(1):1-6
An iterative extended Hückel molecular orbital calculation was used to obtain wave functions for the ground state of ferrocene and several low lying states of the ferrocenium ion. Photoemission spectra in terms of relative ionization potentials and the electric field gradient at the iron nucleus were calculated for ferrocene andg values and the electric field gradient were calculated for the ferrocenium ion. These values are in good agreement with experiment. The nature of the molecular orbitals was compared with results of previous semi-empirical andab initio calculations. 相似文献
13.
Search on ruggedness of fast gas chromatography-mass spectrometry in pesticide residues analysis 总被引:1,自引:0,他引:1
Kirchner M Matisová E Otrekal R Hercegová A de Zeeuwb J 《Journal of chromatography. A》2005,1084(1-2):63-70
In this study, suitability of fast gas chromatography-mass spectrometry (GC-MS) on a narrow-bore column with a programmed temperature vaporizer for the analysis of pesticide residues in non-fatty food was evaluated. The main objectives were ruggedness and stability of chromatographic system with regards to co-extractives injected. The chromatographic matrix induced response enhancement was found to be strongly dependent on the concentration of residues and is reaching up to 700% compared to the pesticides solutions in a neat solvent. However, the responses of pesticides in matrix-matched standards at different concentration levels do not significantly change during 130 injections. Response enhancement/or decrease is influenced by the sample preparation technique. External calibration with matrix-matched calibration standards should, therefore, provide results with good precision also at the concentration level of 0.005 mg kg(-1). Special attention is given to the performance of the chromatographic column and retention gap with regards to peak widths, peak tailing and different sample preparation methods. During approximately 460 matrix sample injections, the performance of the analytical column was acceptable. GC-MS set-up with 0.15 mm i.d. column can be successfully utilized for the pesticide residues analysis. 相似文献
14.
Le Guennic B Kirchner B Reiher M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(24):7448-7460
In several recent studies Schrock and collaborators demonstrated for the first time how molecular dinitrogen can be catalytically transformed under mild and ambient conditions to ammonia by a molybdenum triamidoamine complex. In this work, we investigate the geometrical and electronic structures involved in this process of dinitrogen activation with quantum chemical methods. Density functional theory (DFT) has been employed to calculate the coordination energies of ammonia and dinitrogen relevant for the dissociation/association step in which ammonia is substituted by dinitrogen. In the DFT calculations the triamidoamine chelate ligand has been modeled by a systematic hierarchy of increasingly complex substituents at the amide nitrogen atoms. The most complex ligand considered is an experimentally known ligand with an HMT = 3,5-(2,4,6-Me3C6H2)2C6H3 substituent. Several assumptions by Schrock and collaborators on key reaction steps are confirmed by our calculations. Additional information is provided on many species not yet observed experimentally. Particular attention is paid to the role of the charge of the complexes. The investigation demonstrates that dinitrogen coordination is enhanced for the negatively charged metal fragment, that is, coordination is more favorable for the anionic metal fragment than for the neutral species. Coordination of N2 is least favorable for the cationic metal fragment. Furthermore, ammonia abstraction from the cationic complex is energetically unfavorable, while NH3 abstraction is less difficult from the neutral and easily feasible from the anionic low-spin complex. 相似文献
15.
Martin Kirchner Walter Schnelle Frank R. Wagner Rüdiger Kniep Rainer Niewa 《无机化学与普通化学杂志》2005,631(8):1477-1486
Single phase powders of (A19N7)[In4]2 (A = Ca, Sr) and (Ca4N)[In2] were prepared by reaction of melt beads of the metallic components with nitrogen. The crystal structure of (Ca19N7)[In4]2 was refined based on neutron and X‐ray powder diffraction data. The crystal structure of (Sr19N7)[In4]2 was solved from the X‐ray powder pattern. The structure refinements in combination with results from chemical analyses ascertain the compositions. The compounds (A19N7)[In4]2 (A = Ca, Sr) are isotypes of (Ca19N7)[Ag4]2; (Ca19N7)[In4]2 is probably identical to the earlier reported (Ca18.5N7)[In4]2. The crystal structure of the isotypes (A19N7)[In4]2 (A = Ca, Sr; cubic, , Ca: a = 1471.65(3) pm; Sr: a = 1561.0(1) pm) contains isolated [In4] tetrahedra embedded in a framework of edge‐ and vertex‐sharing (A6N) octahedra. Six of these octahedra are condensed by edge‐sharing around one central A2+ ion to form “superoctahedra” (A19N6) which are connected three‐dimensionally via further octahedra by corner‐sharing. The crystal structure of (Ca4N)[In2] (tetragonal, I41/amd, a = 491.14(4) pm, c = 2907.7(3) pm) consists of alternating layers of perovskite type slabs of vertex‐sharing octahedra (Ca2Ca4/2N) and parallel arranged infinite zigzag chains equation/tex2gif-stack-1.gif[In2]. In the sense of Zintl‐type counting the compounds (A2+)19(N3?)7[(In2.125?)4]2 present an electron excess, (Ca2+)4(N3?)[(In2.5?)2] is electron deficient. Metallic properties are supported by electrical resistivity and magnetic susceptibility measurements. The analysis of the electronic structures gives evidence for the existence of homoatomic interactions In–In and significant heteroatomic metal–metal interactions Ca–In which favor the deviations of the title compounds from the (8 – N) rule. 相似文献
16.
Metal–organic frameworks (MOFs) gain increasing interest due to their outstanding properties like extremely high porosity, structural variability, and various possibilities for functionalization. Their overall structure is usually determined by diffraction techniques. However, diffraction is often not sensitive for subtle local structural changes and ordering effects as well as dynamics and flexibility effects. Solid-state nuclear magnetic resonance (ssNMR) spectroscopy is sensitive for short range interactions and thus complementary to diffraction techniques. Novel methodical advances make ssNMR experiments increasingly suitable to tackle the above mentioned problems and challenges. NMR spectroscopy also allows study of host–guest interactions between the MOF lattice and adsorbed guest species. Understanding the underlying mechanisms and interactions is particularly important with respect to applications such as gas and liquid separation processes, gas storage, and others. Special in situ NMR experiments allow investigation of properties and functions of MOFs under controlled and application-relevant conditions. The present minireview explains the potential of various solid-state and in situ NMR techniques and illustrates their application to MOFs by highlighting selected examples from recent literature.Metal–organic frameworks (MOFs) gain increasing interest due to their outstanding properties like extremely high porosity, structural variability, and various possibilities for functionalization. 相似文献
17.
Sieber A Boskovic C Bircher R Waldmann O Ochsenbein ST Chaboussant G Güdel HU Kirchner N van Slageren J Wernsdorfer W Neels A Stoeckli-Evans H Janssen S Juranyi F Mutka H 《Inorganic chemistry》2005,44(12):4315-4325
A new family of tetranuclear Ni complexes [Ni(4)(ROH)(4)L(4)] (H(2)L = salicylidene-2-ethanolamine; R = Me (1) or Et (2)) has been synthesized and studied. Complexes 1 and 2 possess a [Ni(4)O(4)] core comprising a distorted cubane arrangement. Magnetic susceptibility and inelastic neutron scattering studies indicate a combination of ferromagnetic and antiferromagnetic pairwise exchange interactions between the four Ni(II) centers, resulting in an S = 4 spin ground state. Magnetization measurements reveal an easy-axis-type magnetic anisotropy with D approximately -0.93 cm(-)(1) for both complexes. Despite the large magnetic anisotropy, no slow relaxation of the magnetization is observed down to 40 mK. To determine the origin of the low-temperature magnetic behavior, the magnetic anisotropy of complex 1 was probed in detail using inelastic neutron scattering and frequency domain magnetic resonance spectroscopy. The spectroscopic studies confirm the easy-axis-type anisotropy and indicate strong transverse interactions. These lead to rapid quantum tunneling of the magnetization, explaining the unexpected absence of slow magnetization relaxation for complex 1. 相似文献
18.
The cubic inverse Perovskites (Eu3O)In and (Eu3O)Sn were prepared from the metals and Eu2O3 or SnO2, respectively. For (Eu3O)In the crystal structure analysis was performed on single crystal X‐ray diffraction data (space group , a = 512.79(3) pm, Z = 1, Rgt(F) = 0.022, wR(F2) = 0.044). The data indicated full occupancy on all sites and a fully ordered structure. According to magnetic susceptibility measurements and X‐ray absorption spectroscopic data at the Eu LIII edge both compounds contain europium in the 4f7 (Eu2+) electronic state. (Eu3O)In orders ferromagnetically at 185(5) K, (Eu3O)Sn shows antiferromagnetic order at 31.4(2) K. Both compounds behave as metallic conductors in electrical resistivity measurements. However, (Eu3O)In may be classified a metal, while (Eu3O)Sn is more likely a heavily doped degenerated semiconductor or semimetal according to the absolute values of the resistivity. 相似文献
19.
E. Wiegel und H. H. Kirchner 《Fresenius' Journal of Analytical Chemistry》1963,195(2):97-113
Zusammenfassung Die bereits an aliphatischen Alkoholen und Ketonen mit Hilfe eines selbstregistrierenden Infrarotspektralphotometers durchgeführten Untersuchungen zur infrarotspektroskopischen Erfassung kleiner Wassergehalte wurden an den mit Wasser mischbaren organischen Lösungsmitteln Äthylenglykol, Äthylenglykolmonomethyläther, Äthylenchlorhydrin, Glycerin, 1,4-Dioxan und Benzylalkohol fortgesetzt. Für Wasserbestimmungen in diesen Lösungsmitteln erwies sich besonders die OH-Kombinationsschwingung des Wassers im Spektralbereich um 5200 cm–1 geeignet. Mit Hilfe dieser OH-Absorptionsbande, die Messungen in Küvetten mit Glasfenstern gestattet, können im Direktverfahren Wassergehalte von etwa 1,0–10,0 Vol-% mit guter Genauigkeit, besser als 0,1 Vol-% bestimmt werden; im Kompensationsverfahren sind noch Konzentrationen von 0,1–2,0 Vol-% erfaßbar.Bei dem nicht hydroxylhaltigen 1,4-Dioxan lassen sich mittels dieser Bande Wassergehalte von 0,1–10,0 Vol-% im Direktverfahren bestimmen. Für die quantitative Erfassung sehr kleiner Wassergehalte im Dioxan eignet sich infolge günstiger Eigenabsorptionsverhältnisse besonders gut die OH-Valenzschwingung bei 3600 cm–1, die hier Wasser-bestimmungen bis herab zu 0,02 Vol-% im Direktverfahren mit hinreichender Genauigkeit ermöglicht.Auch die OH-Deformationsschwingung bei 1600 cm–1 erweist sich für Wassergehalte von 0,5–10 Vol-% zum qualitativen Nachweis und zur quantitativen Bestimmung verwendbar, soweit bei den betreffenden Lösungsmitteln nicht Fehler durch die Löslichkeit der Steinsalz-Küvettenfenster auftreten.Frühere Mitt.: Wiegel, E., u. H. H. Kirchner: diese Z. 178, 241 (1960/61). 相似文献
20.