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High temperature scanning tunneling spectroscopy (HT-STS) was used to investigate the electronic structure of Au(1 1 1) at different temperatures in the energy range 0-1 eV below the Fermi level. We concentrated on the influence of temperature on the Shockley surface state (SS) appearing on noble metals surface due to a surface projected bulk bang gap in [1 1 1] direction. The influence of temperature on the projected band gap edge (BE) was also investigated. The experiment was carried out in the temperature range 294-580 K. As the result of the experiment a delicate shift of the SS and the BE in direction of the Fermi level was reported. 相似文献
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Sticking probability for oxygen adsorption on thin iron films and readsorption on surface sites liberated due to incorporation of the adsorbate adatoms below the surface during thermal treatment has been studied by means of the Wagener flow method. Sticking probability for oxygen adsorption on oxidized thin iron films has also been measured for comparison.
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María Beatriz de la Calle Guntiñas Michiel Ceulemans Claudia Witte Ryszard Łobiński Freddy C. Adams 《Mikrochimica acta》1995,120(1-4):73-82
A method is presented for the selective determination of the volatile selenium species dimethylselenide and dimethyldiselenide, using a commercially available purge-and-trap injection system coupled to capillary gas chromatography-microwave induced plasma-atomic emission spectrometry. The efficiency of the purging step was evaluated and the parameters affecting the purge and trap processes were optimized. The method was applied to the determination of volatile selenium compounds in lake water. Relative detection limits of 2ng/l for dimethylselenide and dimethyldiselenide, corresponding to an absolute detection limit of 10 pg, were achieved. 相似文献
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Mulrooney CA Li X DiVirgilio ES Kozlowski MC 《Journal of the American Chemical Society》2003,125(23):6856-6857
By using oxygen as the terminal oxidant, copper complexes derived from chiral 1,5-diaza-cis-decalin catalyze the enantioselective oxidative biaryl coupling of highly functionalized naphthols to provide octa- and decasubstituted binaphthalenes with high selectivity (86-90% ee). Products containing very electron-rich naphthalenes were prone to epimerization under the reaction conditions. This epimerization could be suppressed by employing naphthol starting materials with phenol protecting groups that attenuated the electron-rich nature of the naphthalenes. Direct oxidation of the resultant chiral 1,1'-binaphthol framework completed the first asymmetric synthesis of a perylenequinone containing only an axial chirality element. 相似文献
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An analytical derivation of multicenter and multiparticle integrals for explicitly correlated Cartesian Gaussian-type cluster functions is demonstrated. The evaluation method is based on the application of raising operators that transform spherical cluster Gaussian functions into Cartesian Gaussian functions. 相似文献
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Local density and generalized gradient approximation time-dependent density functional methods have been used for calculation of the singlet and triplet excited states of nickel-porphine, Ni-tetraphenyloporphine, and Ni-octaethyloporphyrine. Special attention is paid to metal-ligand transitions and d-d transitions. It is shown that the lowest exited singlet states of the three compounds can be described as a transfer of an electron from the porphine ring to the d(x2-y2) orbital of the nickel atom. On the other hand, the lowest excited triplet state arises from promotion of an electron between two nickel d orbitals, an occupied d(z2) and an empty d(x2-y2). It is proposed that a rapid quenching of the excited singlet states is due to an ultrafast intersystem crossing between 1Eg)and 3Eg or 3B1g states. 相似文献
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A new complex of bis-axially coordinated iron(II) phthalocyanine by 4-cyanopyridine (4-CNpy) has been obtained in crystalline form as an adduct with two 4-CNpy molecules. The [FePc(4-CNpy)2] · 2(4-CNpy) crystallises in the monoclinic system, space group P21/c with two molecules in the unit cell. The iron(II) coordinates four isoindole nitrogen atoms of the almost planar phthalocyaninato(2−) macroring and axially two nitrogen atoms of 4-CNpy molecules. The coordination polyhedron around the Fe(II) atom approximates to a tetragonal by-pyramid. Four equatorial Fe–N bonds are shorter (1.936(2) Å) than two axial Fe–N bonds (2.027(2) Å). The centrosymmetric FePc(4-CNpy)2 molecules form alternating sheets parallel to the bc crystallographic plane and solvated 4-CNpy molecules that are anti-parallel oriented by their polar cyano groups are located between the sheets of FePc(4-CNpy)2 molecules. Ligation of the intermediate-spin iron(II) phthalocyanine by 4-CNpy molecules leads to the low spin Fe(II) complex. The importance of the d(π) → π∗(Pc) back donation is manifested in the difference between the values of C–N isoindole and C–N azamethine bond lengths of the Pc macrocycle. The thermal analysis of the crystals of [FePc(4-CN)2] · 2(4-CNpy) shows two steps responsible for a loss of solvated (∼170 °C) and coordinated (∼235 °C) 4-CNpy molecules. 相似文献