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11.
12.
The ab initio molecular fragment approach is applied to a characterization study of the ground state of the zwitterion of glycine. Included among the properties studied are the — conformational energy surface, the electronic structure, and the magnitude and direction of the dipole moment. The results of the present study are compared to the results of other theoretical and experimental studies.This work was supported in part by the National Science Foundation, the University of Kansas, and the Upjohn Company, Kalamazoo, Michigan 49001.NSF Trainee (1969-1972).Alfred P. Sloan Research Fellow (1971–1973). 相似文献
13.
Ronald N. Warrener Richard P. Johnson Charles W. Jefford David A. Ralph 《Tetrahedron letters》1979,20(31):2939-2942
Structural assignments are made to the three adducts derived from the title reaction. 1H-n.m.r., 13C-n.m.r. and euroshift data are used to support the new structures. 相似文献
14.
Kohji Chihara Takeshi Takemura Tsuguo Yamaoka N. Yamamoto Arnold Schaffer Ralph S. Becker 《Photochemistry and photobiology》1979,29(5):1001-1008
Abstract— The absorption and emission spectra, lifetimes and quantum yields of all-trans retinol have been examined as a function of solvent and temperature. In addition, the spectroscopy of retinyl ether and 2 other polyene alcohols have been determined. Based on the results obtained, we conclude that the singlet excited state of retinol and retinyl cther is of a forbidden character and of the type loosely called 1 A- g . Retinol forms a dimer in an alkane solvent when cooling from 298 to 77 K. A general structure for the dimer is proposed. 相似文献
15.
Volatile hydrides of As, Se, Sb, Sn and Bi were generated from aqueous sample solutions using a tetrahydroborate reductant. The gaseous analytes were transferred to the inner wall of an electrothermal vaporizer (graphite furnace) and preconcentrated on a 1.25 μg thin-film of reduced palladium at 400°C. The furnace comprised the sample introduction unit of an inductively coupled plasma mass spectrometric detection system. Absolute limits of detection (3σB) were 2.9, 3.3, 54, 5 and 1980 pg for As, Sb, Sn, Bi and Se, respectively. System efficiency for the generation and sequestration of the hydrides averaged, with the exception of Se, better than 75%. Multielement determinations of As, Se and Bi were possible using the same experimental conditions, those for Sn and Sb were accomplished in a separate run. The efficacy of this analytical approach was verified by the analysis of several marine reference materials using simple calibration standards prepared in the same manner as the samples. Good agreement with certified values was achieved for As, Sn, Sb and Se; no reference materials were available for assessment of accuracy in the case of Bi. 相似文献
16.
The performance of single-drop microextraction (SDME), coupled with gas chromatography/mass spectrometry, was assessed for the determination of tributyltin compounds in water and solid samples. Experimental parameters impacting the performance of SDME, such as microextraction solvent and sampling and stirring time, were investigated. Analytical results obtained by SDME were compared with those generated by conventional solid phase microextraction (SPME) and liquid-liquid extraction (LLE) for the determination of TBT in PACS-2 sediment certified reference material (CRM). 相似文献
17.
The ligand‐exchange mechanism of solvated Be2+ cations has been studied by means of DFT calculations (RB3LYP/6‐311+G**). Ligand exchange around [BeL4]2+, where L=H2O, NH3, CO2, formaldehyde (H2CO), HCN, N2, and CO, was found to follow an associative interchange (Ia) process in all cases. The size of the activation barrier is almost independent of the type of donor atom, and depends mainly on the hybridization undergone by the donor atom. This, in turn, suggests that steric effects play a major role in solvent‐ and ligand‐exchange reactions in Be2+ systems. 相似文献
18.
Ralph de Laubenfels 《Semigroup Forum》1986,33(1):257-263
We show that a linear operator (possibly unbounded), A, on a reflexive Banach space, X, is a scalar-type spectral operator, with non-negative spectrum, if and only if the following conditions hold.
- A generates a uniformly bounded holomorphic semigroup {e?zA}Re(z)≥0.
- If \(F_N (s) \equiv \int_{ - N}^N {\tfrac{{\sin (sr)}}{r}} e^{irA} dr\) , then {‖FN‖} N=1 ∞ is uniformly bounded on [0,∞) and, for all x in X, the sequence {FN(s)x} N=1 ∞ converges pointwise on [0, ∞) to a vector-valued function of bounded variation.
19.
J. D. Petke Gerald M. Maggiora‡ Lester Shipman‡ Ralph E. CHRISTOFFERSEN‡ 《Photochemistry and photobiology》1979,30(2):203-223
Abstract— Ab initio configuration interaction wavefunctions and energies are reported for the ground state and many low-lying excited singlet and triplet states of ethyl pheophorbide a (Et-Pheo a) and ethyl chlorophyllide a (Et-Chl a), and are employed in an analysis of the electronic absorption spectra of these systems. In both molecules the visible spectrum is found to consist of transitions to the two lowest-lying 1(π, π*) states, S1 and S2. The configurational compositions of S1 and S2 in both molecules are similar, and are described qualitatively in terms of a four-orbital model. The S1← S0 transition in each case is predicted to be intense, and is largely in-plane y-polarized, while the S2← S0 transition is predicted to be extremely weak and in-plane polarized. The orientation of the S2← S0 transition dipole is not conclusively established in the present calculations. The Soret band in both molecules is composed of transitions to no less than ten states (S3-S12 in Et-Chl a and S3-S7S9-S12. and S14 in Et-Pheo a), which exhibit primarily (π, π*) character. The configurational compositions of these states are generally a complex mixture of excitations from both occupied macrocyclic π molecular orbitals and occupied orbitals with electron density in the cyclopen-tanone ring and the carbomethoxy chain. No clear correspondences are evident between respective Soret states of the two systems. Transitions to these states are generally intense and display a variety of in-plane polarizations. Two additional Soret states of Et-Pheo a, S8 and S13, exhibit primarily (n. π*) character. S8 is characterized by excitations from u and non-bonding regions of the carbomethoxy chain, while S13 is described by n →π* excitations involving the nitrogen atom of ring II. No corresponding (n, π*) states were found for Et-Chl a. In both molecules the lowest two triplet states, T1 and T2, are found to lie lower in energy than S1. while T, and S1 are approximately degenerate. The configurational compositions of T1-T4 of both molecules are nearly identical, and may be described by a four-orbital model. However, the compositions of T1-T4 differ sharply from those of S1 and S2. A number of higher-lying 3(π, π*) states of both molecules (T5-T13 in Et-Chi a and T8-T9, T11-T13 in Et-Pheo a) are found to have energies similar to the singlet Soret states, relative to S0. They are characterized by a complex mixture of configurations which do not include significant contributions involving the four-orbital model. In addition, two 3(n, π*) states of Et-Pheo a, T10 and T14, are found, which are somewhat analogous to S8 and S13. Additional data presented include the charge distributions and molecular dipole moments of the S0. S1, and T1 states of both molecules, as well as energies and oscillator strengths of computed Sn←S1 and Tn←1 transitions. 相似文献
20.
Puzenko A Hayashi Y Ryabov YE Balin I Feldman Y Kaatze U Behrends R 《The journal of physical chemistry. B》2005,109(12):6031-6035
We discuss the relaxation dynamics of glycerol-water mixtures, as studied by dielectric spectroscopy in the frequency range from 1 Hz to 250 MHz and at temperatures between 173 and 323 K. The experimental results obtained for the glycerol-rich mixtures suggest that the main dielectric relaxation process, as well as the so-called high-frequency "excess wing" (EW) and dc conductivity, follow the same temperature dependence. This result indicates that all of these processes are induced by the same molecular origin. A new phenomenological function is proposed to describe the whole dielectric spectrum in the covered frequency range, and some possible mechanisms of dielectric behaviors through the dc conductivity, the main relaxation process, and the EW are discussed. 相似文献