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1.
2.
The development and the use of the diamond anvil cell for Mössbauer Spectroscopy (MS) to pressures nearing 100 GPa are discussed. Three types of cells and their typical performance are given. Pressure calibration, hydrostatic media, gasketing, collimation, -ray absorption, and sample size for MS are reviewed. New MS results showing hysteresis in the room temperature high pressure transition in iron and showing the rapid rise ofT
N in NiI2 with pressure are presented. 相似文献
3.
4.
We report the first high pressure129I Mössbauer measurements with elemental iodine at pressures to 30 GPa. A 20 mg/cm2
129I2 absorber was mounted in a diamond anvil cell with an effective diameter of 0.21 mm. The source used was Mg3
129mTeO6. Experiments were performed mainly at 4 K and the pressure was monitored by the ruby fluorescence method. With increasing pressure we observe a gradual decrease in ¦e2qQ¦ and an increase in IS and values of the low pressure, molecular phase; at 16 GPa a new phase (HP1) is detected characterized by a change in sign of e2qQ and a smaller value of ¦e2qQ¦, and a substantial increase in . At 24 GPa a new phase (HP2) is formed that is characterized by a smaller value of . In general the population of the molecular phase decreases from 1.0 near 15 GPa to a value of 0.4 at 30 GPa. The fraction of the high pressure phase (HP1 + HP2) increases at the expense of the molecular phase and that of the HP2 at the expense of the HP1 phase. These observations are discussed in relation to the onset of a metallic phase near 16 GPa and recent x-ray diffraction studies.Work performed under the auspices of the U.S. Department of Energy. 相似文献
5.
Spectral quantities of cyclopropane, cyclobutane, cyclohexane, and of several derivatives, have been calculated by a semiempirical all-valence electron SCF-CI MO method. In cyclopropane, HOMO is practically localized in the carbon-frame, and LVMO is purely so. In cyclobutane, these two MO's are based on C-H bonds, while cyclohexane holds an intermediate position. Despite the overall similarity-experimental and computed-of the spectra of these molecules, assignments are non-parallel. Like cyclopropane, cyclobutane can extend conjugation, but to a diminished degree; cyclohexane behaves in this respect like an acyclic alkane. An interpretation of this gradation, in terms of the nature of high-lying MO's, is proposed. 相似文献
6.
Pavel V. Pasternak 《Journal of fluorine chemistry》2004,125(12):1853-1868
A new CF2X-analogue of 1,1-bis(trifluoromethyl)-2,2-dicyanoethylene (X = P(O)(OEt)2), diethyl (1,1-difluoro-3,3-dicyano-2-trifluoromethylallyl)phosphonate, has been synthesized from diethoxyphosphoryl pentafluoroacetone 1. A similar phosphoryl analogue of ethyl 3,3-dicyano-2-trifluoromethylacrylate, ethyl 3,3-dicyano-2-[(diethoxyphosphoryl)difluoromethyl]acrylate, has been obtained from ethyl 3-(diethoxyphosphoryl)-3,3-difluoro-2-oxopropionate 2. By heterocyclization of these new ethylenes with 3-methyl-2-pyrazoline-5-ones, 3(5)-aminopyrazoles, dimedone, 2-aminopyridines, 1-aryl-3-methyl-5-aminopyrazoles, 1,3,3-trimethylisoquinolines, as well as by condensation with anilines and ketones, the difluoromethylphosphonate-substituted derivatives of 1,4-dihydropyrano[2,3-c]pyrazole, 4,5-dihydropyrazolo[1,5-a]pyrimidine, 5,6,7,8-tetrahydro-4H-chromene, 2H-pyrido[1,2-a]pyrimidine, 4,7-dihydro-1H-pyrazolo[3,4-b]pyridine, 1,4-dihydropyridine, 4,5,6,7-tetrahydro-1H-[1]pyrindine, 1,4,5,6,7,8-hexahydroquinoline, and 6,7-dihydro-2H-pyrido[2,1-a]isoquinoline have been obtained in one stage. 相似文献
7.
The molecular spin–orbit coupling operator is brought into a simplified form through a convenient choice of origin for the orbital angular momentum operator. The eigenvalue problem of the Hamiltonian that includes the spin–orbit (SOC ) operator as a perturbation is solved by means of a linear variational procedure in the basis of the spin-pure molecular eigenstates. Test calculations on benzophenone are presented and the results are compared to experiment. We discuss the minimal size of the spin-pure variational basis needed to achieve stable results as well as the amount of single-excitation configurational mixing needed to describe the spin-pure molecular eigenstates. 相似文献
8.
U. Klinsmann J. Gauthier K. Schaffner M. Pasternak B. Fuchs 《Helvetica chimica acta》1972,55(7):2643-2659
In continuation of previous work on cyclopentadienone dimers [3], thermal and photochemical interconversions of the isomeric diketones 1, 3 , and 5 by skeletal rearrangements have been established to the extent summarized in schemes 2 and 3, and the intramolecular [2+2] cycloaddition 1 → 2 was found to be reversible photochemically. 相似文献
9.
Thien Y Vu Prof. Anna Chrostowska Prof. Thi Kieu Xuan Huynh Prof. Saïd Khayar Prof. Alain Dargelos Katarzyna Justyna Dr. Beata Pasternak Prof. Stanisław Leśniak Prof. Curt Wentrup 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(44):14983-14988
Thermal reactions of N‐benzylidene‐ and N‐(2‐pyridylmethylidene)‐tert‐butylamines ( 5 and 13 ) under FVT conditions have been investigated. Unexpectedly, at 800 °C, compound 5 yields 1,2‐dimethylindole and 3‐methylisoquinoline. In the reaction of 13 at 800 °C, 3‐methylimidazo[1,5‐a]pyridine was obtained as the major product. Mechanisms of these reactions have been proposed on the basis of DFT calculations. Furthermore, UV‐photoelectron spectroscopy combined with FVT has been applied for direct monitoring and characterization of the thermolysis products in situ. 相似文献
10.