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91.
Quantum chemical calculations with gradient-corrected (B3LYP) density functional theory for the mono- and bispentazolato complexes of the first row transition metals (V, Cr, Mn, Fe, Co, and Ni), the all-nitrogen counterparts of metallocenes, were performed, and their stability was investigated. All possible bonding modes (e.g. eta1, eta2, eta3, and eta5) of the pentazolato ligand to the transition metals have been examined. The transition metal pentazolato complexes are predicted to be strongly bound molecules. The computed total bond dissociation enthalpies that yield free transition metal atoms in their ground states and the free pentazolato ligands were found in the range of 122.0-201.9 (3.7-102.3) kcal mol(-1) for the bispentazolato (monopentazolato) complexes, while those yielding M2+ and anionic pentazolato ligands were found in the range of 473.2-516.7 (273.6-353.5) kcal mol(-1). The electronic ground states of azametallocenes along with their spectroscopic properties (IR, NMR, and UV-vis) obtained in a consistent manner across the first transition metal series provide means for discussion of their electronic and bonding properties, the identification of the respective azametallocenes, and future laboratory studies. Finally, exploring synthetic routes to azametallocenes it was found that a [2 + 3] cycloaddition of dinitrogen to a coordinated azide ligand with nickel(II) does not seem to provide a promising synthetic route for transition metal pentazolato complexes while the oxidative addition of phenylpentazole and fluoropentazole to Ni(0) bisphosphane complexes merits attention for the experimentalists. 相似文献
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Paraskevi Pouli Giannis Bounos Savas Georgiou Costas Fotakis 《Applied Surface Science》2008,254(21):6875-6879
Despite significant advances, laser ablation with nanosecond pulses presents limitations in dealing with the restoration of classes of painted works of art, such as paintings with a very thin layer of varnish. Femtosecond laser processing promises the means for overcoming such limitations. To this end, femtosecond ablation of two typical varnishes, dammar and mastic, is examined. For these varnishes, processing by Ti:Sapphire irradiation (800 nm) turns out to be ineffective. In contrast, irradiation with 248 nm ∼500 fs laser pulses results in a higher etching resolution (etching rates of ∼1 μm/pulse or less). For irradiation with few laser pulses at moderate laser fluences, etched morphology is far smoother than in the processing with nanosecond laser pulses. Furthermore, chemical modifications are considerably reduced (by nearly an order of magnitude), and exhibit a number of additional novel differences. Both etching rates and extent of chemical modifications are largely independent of varnish absorptivity. In all, femtosecond UV laser irradiation is indicated to hold a high potential, offering new perspectives for the restoration of painted works of art. Finally, a tentative model is advanced accounting in a consistent way for the observations. 相似文献
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Inglis R White F Piligkos S Wernsdorfer W Brechin EK Papaefstathiou GS 《Chemical communications (Cambridge, England)》2011,47(11):3090-3092
A [Mn(III)(9)] partial supertetrahedron is a Single-Molecule Magnet (SMM) with an energy barrier to magnetisation reversal of ~30 K and represents the first chiral SMM obtained from achiral starting materials. 相似文献
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The Reaction of Bunsen's Cacodyl Disulfide,Me2As(S)‐S‐AsMe2, with Iodine: Preparation and Properties of Dimethylarsinosulfenyl Iodide,Me2As‐S‐I 下载免费PDF全文
Panayiotis V. Ioannou Dimitris G. Vachliotis Athanassios Chrissanthopoulos 《无机化学与普通化学杂志》2015,641(7):1340-1346
Bunsen's cacodyl disulfide, Me2As(S)‐S‐AsMe2 ( 1 ), reacted with iodine giving the novel dimethylarsinosulfenyl iodide, Me2As‐S‐I ( 3 ) although theoretical calculations indicated that the AsV compound Me2As(S)‐I ( 4 ) was more stable in the gas phase. The oily product was stable neat and as a solution in CDCl3 at +4 °C and –20 °C for at least 15 d. Light, H2O, H2O2, and Zn dust, but not NaI or Ag, decomposed it. Compound 3 did not interact with Ph3N, with Ph2NH and PhNH2 it interacted but not reacted. 3 was decomposed by piperidine, with pyridine and 4‐dimethylaminopyridine it interacted and produced Me2As‐SS‐AsMe2 ( 2 ) and I2 that formed charge transfer complexes Base · I2, whereas Et3N decomposed 3 , and 3Et3N · 2I2 was isolated. 3 was desulfurized by Ph3P and (Me2N)3P completely, and by (PhO)3P and (PhS)3P partially. The reactions of 3 with (Me2N)3P, (PhS)3P, and (EtO)3P were complicated. From the AsIII nucleophiles, only Ph3As was bound, while (PhS)3As reacted slowly in a complicated manner with 3 . No interaction of 3 with MeOH or PhOH was observed but NaOH, Ag2O, and PhONa decomposed it. Thiophenol produced traces of Me2As‐SPh ( 10 ) and sodium thiophenolate attacked mainly at AsIII of 3 . Thus, externally stabilized sulfenium ions of the type Me2As‐S‐Nu+I– were not obtained. 相似文献
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Dr. Logesh Mathivathanan Dr. Guillaume Rogez Dr. Nadia Ben Amor Prof. Vincent Robert Prof. Raphael G. Raptis Dr. Athanassios K. Boudalis 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(56):12769-12784
Previously reported ferromagnetic triangles (NnBu4)2[Cu3(μ3-Cl)2(μ-4-NO2-pz)3Cl3] ( 1 ), (PPN)2[Cu3(μ3-Cl)2(μ-pz)3Cl3] ( 2 ), (bmim)2[Cu3(μ3-Cl)2(μ-pz)3Cl3] ( 3 ) and newly reported (PPh4)2[Cu3(μ3-Cl)2(μ-4-Ph-pz)3Cl3] ( 4 ) were studied by magnetic susceptometry, electron paramagnetic resonance (EPR) spectroscopy and ab initio calculations to assess the origins of their ferromagnetism and of the magnetic anisotropy of their ground S=3/2 state (PPN+=bis(triphenylphosphine)iminium, bmim+=1-butyl-3-methylbenzimidazolium, pz−=pyrazolate). Ab initio studies revealed the d character of the magnetic orbitals of the compressed trigonal bipyramidal copper(II) ions. Ferromagnetic interactions were attributed to weak orbital overlap via the pyrazolate bridges. From the wavefunctions expansions, the ratios of the magnetic couplings were determined, which were indeterminate by magnetic susceptometry. Single-crystal EPR studies of 1 were carried out to extend the spin Hamiltonian with terms which induce zero-field splitting (zfs), namely dipolar interactions, anisotropic exchange and Dzyaloshinskii–Moriya interactions (DMI). The data were treated through both a giant-spin model and through a multispin exchange-coupled model. The latter indicated that ≈62 % of the zfs is due to anisotropic and ≈38 % due to dipolar interactions. The powder EPR data of all complexes were fitted to a simplified form of the multispin model and the anisotropic and dipolar contributions to the ground state zfs were estimated. 相似文献