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41.
The reflection of the conduction electrons from surfaces of a thin (d = 100 μm) monocrystalline plate of tungsten [(110) face] is investigated by the method of static skin effect. It is found that by heating the crystal in vacuum up to 2500 °K, the oxide layer is removed and the specular reflection of the conductive electrons increases. The adsorption of the monomolecular layers of barium and copper atoms markedly increases diffuse reflection. A resonance mechanism of carrier interaction in the metal with adsorbed atoms is discussed. 相似文献
42.
43.
Natalja Vogt Rainer Rudert Anatolii N. Rykov Nikolai M. Karasev Igor F. Shishkov Jürgen Vogt 《Structural chemistry》2011,22(2):287-291
The gas-phase electron diffraction (GED) experiment at the Moscow State University was carried out for the first time using
imaging plates (IPs). The response of the Fuji BAS-MP IPs calibrated by means of 14C standard sources was found to be linear in a broad dynamic interval (larger than 104). The GED study of tetrachloromethane was carried out in order to test the applied technique (IP reader FLA7000) and the
developed software. The determined structural parameters of the CCl4 molecule are in excellent agreement with those obtained in experiments with photographic registration. 相似文献
44.
A. V. Shishkov E. N. Bogacheva 《Russian Journal of Physical Chemistry B, Focus on Physics》2014,8(4):543-548
Advances in studies of protein and complex biological systems by tritium planigraphy are considered. Particular attention is paid to detailing the structural organization of the protein components of the influenza virus. The structure of the M1 protein in a solution, virion, and crystal is analyzed. The specific features of this protein identified using tritium planigraphy and computer simulation are indicative of significant changes in its conformation depending on the “phase” state. Models of the spatial structure of the M1 protein in solution and in the virion are proposed. Structural disorder is observed in one of the three domains of this protein. Ideas on the importance of this structure for the multifunctional properties of the protein, such as binding to the membrane and a ribonucleoprotein complex, as well as the transfer of genetic material during viral infection of healthy cells, were suggested. 相似文献
45.
L. V. Khristenko V. M. Senyavin B. V. Lokshin A. L. Vilkova I. F. Shishkov 《Structural chemistry》2013,24(3):775-787
The IR spectra of o- and m-F-C6H4OCF3 in the gas, liquid, and solid (glass and crystal) phases were analyzed along with the Raman spectra of these compounds in the liquid and solid (glass and crystal) phases. This investigation includes both experimental and theoretical studies of the spectra. Vibrational frequencies and normal modes for all possible stable conformers of m- and o-fluoro(trifluoromethoxy)benzene were calculated using B3LYP/cc-pVTZ harmonic quantum-chemical force fields. It was found that m-F-C6H4OCF3 exists as a mixture of the orthogonal and two planar conformers in the gas, liquid, and amorphous solid (glass) phases and as one orthogonal conformer in the crystal state, while o-F-C6H4OCF3 exhibits only one orthogonal conformer in every phase. 相似文献
46.
47.
The disulphides of dithiophosphinic acids (DS) with the general formula R(2)P(S)SSP(S)R(2), where R = C(2)H(5), C(3)H(7), C(5)H(11), C(6)H(5) (I-IV) form coloured complexes of 1:3 stoichiometry with Pd(II). The absorption maxima and molar absorptivities are: a lambda(I) = 302 nm, epsilon(I) = 2.04 x 10(4) 1.mole(-1).cm(-1); lambda(II) = 305 nm, epsilon(II) = 2.58 x 10(4); lambda(III) = 303 nm, epsilon(III) = 2.60 x 10(4); lambda(IV) = 315 nm, epsilon(IV) = 3.25 x 10(4). The reaction takes about 3 min at room temperature, and the colour is stable for 24 hr. The influence of time, pH, reagent concentration, organic solvents and interferences have been studied. An extractive photometric method of determination of Pd(II) is described and applied to the determination of Pd(II) in a mixture of platinum metals. 相似文献
48.
Olga V. Dorofeeva Yuriy V. Vishnevskiy Natalja Vogt Jürgen Vogt Lyudmila V. Khristenko Sergey V. Krasnoshchekov Igor F. Shishkov István Hargittai Lev V. Vilkov 《Structural chemistry》2007,18(6):739-753
The molecular structure and conformation of nitrobenzene has been reinvestigated by gas-phase electron diffraction (GED), combined analysis of GED and microwave (MW) spectroscopic data, and quantum chemical calculations. The equilibrium r e structure of nitrobenzene was determined by a joint analysis of the GED data and rotational constants taken from the literature. The necessary anharmonic vibrational corrections to the internuclear distances (r e ? r a) and to rotational constants (B e (i) ? B 0 (i) ) were calculated from the B3LYP/cc-pVTZ quadratic and cubic force fields. A combined analysis of GED and MW data led to following structural parameters (r e) of planar nitrobenzene (the total estimated uncertainties are in parentheses): r(C–C)av = 1.391(3) Å, r(C–N) = 1.468(4) Å, r(N–O) = 1.223(2) Å, r(C–H)av = 1.071(3) Å, \({\angle}\)C2–C1–C6 = 123.5(6)°, \({\angle}\)C1–C2–C3 = 117.8(3)°, \({\angle}\)C2–C3–C4 = 120.3(3)°, \({\angle}\)C3–C4–C5 = 120.5(6)°, \({\angle}\)C–C–N = 118.2(3)°, \({\angle}\)C–N–O = 117.9(2)°, \({\angle}\)O–N–O = 124.2(4)°, \({\angle}\)(C–C–H)av = 120.6(20)°. These structural parameters reproduce the experimental B 0 (i) values within 0.05 MHz. The experimental results are in good agreement with the theoretical calculations. The barrier height to internal rotation of nitro group, 4.1±1.0 kcal/mol, was estimated from the GED analysis using a dynamic model. The equilibrium structure was also calculated using the experimental rotational constants for nitrobenzene isotopomers and theoretical rotation–vibration interaction constants. 相似文献
49.
Chotima R Dale T Green M Hey TW McMullin CL Nunns A Orpen AG Shishkov IV Wass DF Wingad RL 《Dalton transactions (Cambridge, England : 2003)》2011,40(19):5316-5323
Reaction of [Pd(PPh(3))(4)] with 1,1-dichloro-2,3-diarylcyclopropenes gives complexes of the type cis-[PdCl(2)(PPh(3))(C(3)(Ar)(2))] (Ar = Ph 5, Mes 6). Reaction of [Pd(dba)(2)] with 1,1-dichloro-2,3-diarylcyclopropenes in benzene gave the corresponding binuclear palladium complexes trans-[PdCl(2)(C(3)(Ar)(2))](2) (Ar = Ph 7, p-(OMe)C(6)H(4)8, p-(F)C(6)H(4)9). Alternatively, when the reactions were performed in acetonitrile, the complexes trans-[PdCl(2)(NCMe)(C(3)(Ar)(2))] (Ar = Ph 10, p-(OMe)C(6)H(4)11 and p-(F)C(6)H(4)) 12) were isolated. Addition of phosphine ligands to the binuclear palladium complex 7 or acetonitrile adducts 11 and 12 gave complexes of the type cis-[PdCl(2)(PR(3))(C(3)(Ar)(2))] (Ar = Ph, R = Cy 13, Ar = p-(OMe)C(6)H(4), R = Ph 14, Ar = p-(F)C(6)H(4), R = Ph 15). Crystal structures of complexes 6·3.25CHCl(3), 10, 11·H(2)O and 12-15 are reported. DFT calculations of complexes 10-12 indicate the barrier to rotation about the carbene-palladium bond is very low, suggesting limited double bond character in these species. Complexes 5-9 were tested for catalytic activity in C-C coupling (Mizoroki-Heck, Suzuki-Miyaura and, for the first time, Stille reactions) and C-N coupling (Buchwald-Hartwig amination) showing excellent conversion with moderate to high selectivity. 相似文献