全文获取类型
收费全文 | 250篇 |
免费 | 9篇 |
国内免费 | 29篇 |
专业分类
化学 | 224篇 |
晶体学 | 1篇 |
力学 | 8篇 |
数学 | 1篇 |
物理学 | 54篇 |
出版年
2024年 | 2篇 |
2023年 | 51篇 |
2022年 | 1篇 |
2021年 | 4篇 |
2020年 | 8篇 |
2019年 | 5篇 |
2018年 | 4篇 |
2017年 | 3篇 |
2016年 | 3篇 |
2015年 | 3篇 |
2014年 | 3篇 |
2013年 | 19篇 |
2012年 | 14篇 |
2011年 | 16篇 |
2010年 | 10篇 |
2009年 | 9篇 |
2008年 | 14篇 |
2007年 | 14篇 |
2006年 | 7篇 |
2005年 | 10篇 |
2004年 | 13篇 |
2003年 | 3篇 |
2002年 | 4篇 |
2001年 | 16篇 |
2000年 | 7篇 |
1999年 | 9篇 |
1998年 | 5篇 |
1997年 | 4篇 |
1996年 | 2篇 |
1995年 | 2篇 |
1994年 | 3篇 |
1993年 | 2篇 |
1992年 | 6篇 |
1991年 | 1篇 |
1990年 | 3篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1986年 | 1篇 |
1981年 | 2篇 |
1979年 | 1篇 |
1977年 | 1篇 |
排序方式: 共有288条查询结果,搜索用时 31 毫秒
1.
J rgen Rosenqvist Kristina Axe Staffan Sj berg Per Persson 《Colloids and surfaces. A, Physicochemical and engineering aspects》2003,220(1-3):91-104
The adsorption of the dicarboxylates o-phthalate, maleate, fumarate, malonate, and oxalate (representing ligands with the general composition −O2C---Cn---CO2−; n=0, 1, or 2) on gibbsite were studied by means of quantitative batch adsorption experiments and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. The interpretations of ATR-FTIR spectra were aided by comparison with IR spectra of solution species and by results from theoretical frequency calculations. The main objectives of the study were to identify the molecular level bonding mechanisms of the dicarboxylates to gibbsite, and to investigate how these were influenced by the composition and structure of the ligands. Carboxylates with n=2 formed predominantly outer sphere complexes, whereas the importance of inner sphere complexes progressively increased for n=1 and 0. The inner sphere structures were identified as mononuclear chelates with one oxygen from each carboxylate group bonded to Al(III) at the surface. This showed the importance of chelate ring structure for the formation of inner sphere surface complexes, with stabilities of the complexes increasing in the order seven-membered ring less than six-membered ring less than five-membered ring. For ligands with n=2 only small variations in surface speciation were observed as a function of steric factors; irrespective of the relative positions of the carboxylate groups and bulkiness of the ligands outer sphere bonding is the dominating adsorption mode. Adsorption experiments were also conducted with gibbsite particles exhibiting differences in shape and surface roughness. These experiments showed that inner sphere complexes were favored on the less well-developed and more irregular gibbsite particles. 相似文献
2.
Per E. M. Siegbahn 《Theoretical chemistry accounts》1994,87(6):441-452
Summary The dihydrides, the difluorides and the dichlorides of the second row transition metal atoms from yttrium to palladium have been studied with methods including electron correlation of all valence electrons. Comparisons are made to the previously studied corresponding diatomic systems. It is found that the general trends of the binding energies of the second hydride and halide remain the same as in the diatomic hydrides and halides. The second ligand binding energies for the dihalides thus vary much more than for the dihydrides. This is due to important attractive effects between the halide lone-pairs and empty 4d-orbitals to the left and strong repulsions towards occupied 4d-orbitals to the right. For some systems the second ligand binds much more than the first ligand, as for RuF2 where the difference is 34.3 kcal/mol, whereas for other systems the reverse is true, as for PdCl2 where the first ligand binds more than the second with 20.4 kcal/mol. The results can be explained by strong ligand field effects and differences in the atomic spectra. 相似文献
3.
Fullerenes分子是科学家在研究碳原子簇过程中发现的一类崭新的有机分子,简单情形是C_(60)。Fullerenes及其衍生物为碳化学打开了—个广阔天地,同时也为固体物理学提供了一个新的研究领域。它还将为材料科学带来新的机会。尽管化学家和物理学家为这类新奇的原子簇勾画了许多理论图象,但关于其键构的—般性规则的研究仍然太少。本文将在 相似文献
4.
多组分聚合物体系中的相容和络合 总被引:5,自引:0,他引:5
在含可控特殊相互作用的多组分聚合物体系中,随着体系中的相互作用密度的增强,体系在本体中可经历由不相容到相容直至络合的不同物理状态。本文概述了相容、络合研究的进展,着重讨论了相容和络合的区别和联系,提出了含氢键相互作用的高分子共混体系中相容-络合转变存在的普遍性。 相似文献
5.
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
6.
D. Mihrin Dr. P. W. Jakobsen A. Voute Dr. L. Manceron Prof. R. Wugt Larsen 《Chemphyschem》2019,20(23):3238-3244
The high-resolution infrared absorption spectrum of the donor bending fundamental band ν of the homodimer (HCN)2 has been collected by long-path static gas-phase Fourier transform spectroscopy at 207 K employing the highly brilliant 2.75 GeV electron storage ring source at Synchrotron SOLEIL. The rovibrational structure of the ν transition has the typical appearance of a perpendicular type band associated with a Σ–Π transition for a linear polyatomic molecule. The total number of 100 assigned transitions are fitted employing a standard semi-rigid linear molecule Hamiltonian, providing the band origin ν0 of 779.05182(50) cm−1 together with spectroscopic parameters for the degenerate excited state. This band origin, blue-shifted by 67.15 cm−1 relative to the HCN monomer, provides the final significant contribution to the change of intra-molecular vibrational zero-point energy upon HCN dimerization. The combination with the vibrational zero-point energy contribution determined recently for the class of large-amplitude inter-molecular fundamental transitions then enables a complete determination of the total change of vibrational zero-point energy of 3.35±0.30 kJ mol−1. The new spectroscopic findings together with previously reported benchmark CCSDT(Q)/CBS electronic energies [Hoobler et al. ChemPhysChem. 19 , 3257–3265 (2018)] provide the best semi-experimental estimate of 16.48±0.30 kJ mol−1 for the dissociation energy D0 of this prototypical homodimer. 相似文献
7.
Valency is defined for each molecular orbital. The molecular orbital valency values are shown to be a good measure of the bonding nature of the molecular orbital. Comparisons are made with photoelectron spectral studies and Mulliken overlap population analysis.The variation of molecular valency and molecular orbital valency with bond angle is studied. It is found that for all the molecules presently considered, energy is linearly related to valency and that the molecular valency reaches a maximum at the equilibrium bond angle. It is also shown that the molecular orbital valency can serve as a quantitatively reliable ordinate for Mulliken-Walsh diagrams. 相似文献
8.
Vinzenz Bachler 《Theoretical chemistry accounts》1997,96(4):223-242
A straightforward procedure is proposed for expanding a molecular orbital determinantal wave function into a set of determinantal
wave functions composed of atomic orbitals localized at the atoms of a molecule. By employing this method, atomic orbital
determinants and their weights can be derived for a molecule from the computed molecular-orbital wave function. The procedure
permits the interpretation of a molecular orbital determinantal wave function in terms of bonding schemes related to the classic
resonance structures used by organic chemists. By using the unrestricted molecular orbital determinant, bonding schemes and
their weights are obtained for butadiene, the butadiene radical cation and the acrylonitrile radical anion. Their dominant
bonding schemes are in accord with the relevant resonance structures for these molecules. For the butadiene radical cation
and the acrylonitrile anion they are shown to be compatible with the accepted mechanisms of the electrochemical coupling reactions
of butadiene and acrylonitrile.
Received: 7 August 1996 / Accepted: 18 March 1997 相似文献
9.
Bernaus A Gaona X Ivask A Kahru A Valiente M 《Analytical and bioanalytical chemistry》2005,382(7):1541-1548
The present work studies the adsorption behaviour of mercury species on different soil components (montmorillonite, kaolinite and humic acid) spiked with CH3HgCl and CH3HgOH at different pH values, by using XAS techniques and bacterial mercury sensors in order to evaluate the availability of methyl mercury on soil components. The study details and discusses different aspects of the adsorption process, including sample preparation (with analysis of adsorbed methyl mercury by ICP-OES), the various adsorption conditions, and the characterization of spiked samples by XAS techniques performed at two synchrotron facilities (ESRF in Grenoble, France and HASYLAB in Hamburg, Germany), as well as bioavailability studies using mercury-specific sensor bacteria. Results show that XAS is a valuable qualitative technique that can be used to identify the bonding character of the Hg in mercury environment. The amount of methyl in mercury adsorbed to montmorillonite was pH-dependent while for all soil components studied, the bond character was not affected by pH. On the other hand, clays exhibited more ionic bonding character than humic acids did with methyl mercury. This interaction has a higher covalent character and so it is more stable for CH3HgOH than for CH3HgCl, due to the higher reactivity of the hydroxyl group arising from the possible formation of hydrogen bonds.The bioavailability of methyl mercury adsorbed to montmorillonite, kaolinite and humic acids was measured using recombinant luminescent sensor bacterium Escherichia coli MC1061 (pmerBRBSluc). In case of contact exposure (suspension assays), the results showed that the bioavailability was higher than it was for exposure to particle-free extracts prepared from these suspensions. The highest bioavailability of methyl mercury was found in suspensions of montmorillonite (about 50% of the total amount), while the bioavailabilities of kaolinite and humic acids were five times lower (about 10%). The behaviour of methyl mercury in the presence of montmorillonite could be explained by the more ionic bonding character of this system, in contrast to the more covalent bonding character observed for humic acids. Thus, XAS techniques seem to provide promising tools for investigating the mechanisms behind the observed bioavailabilities of metals in various environmental matrices, an important topic in environmental toxicology. 相似文献
10.
《Journal of Coordination Chemistry》2012,65(11):1003-1012
A new composite complex of [La(NMP)4(H2O)4][HSiMo12O40]·2NMP·H2O (NMP = N-methyl-2- pyrrolidone) was synthesized and characterized by IR, UV, ESR, TG-DTA and single crystal structural analysis. The water and organic ligands (NMP) coordinate directly with La(III) to form a dodecahedral complex and the SiMo12O4? 40 anion is the counter ion. IR and X-ray analysis show that there is strong interaction between the polyoxometalate and organic donors. The complex is strongly photosensitive under irradiation with sunlight, resulting in a charge-transfer complex by oxidation of the N-methyl-2-pyrrolidone and reduction of the polyoxometalate. Low temperature ESR spectra indicate thermal electron delocalization among the Mo atoms in the title compound. 相似文献