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61.
Stoeffler C Darquié B Shelkovnikov A Daussy C Amy-Klein A Chardonnet C Guy L Crassous J Huet TR Soulard P Asselin P 《Physical chemistry chemical physics : PCCP》2011,13(3):854-863
Originating from the weak interaction, parity violation in chiral molecules has been considered as a possible origin of biohomochirality. We have proposed the observation of molecular parity violation using the two-photon Ramsey fringes technique on a supersonic beam. As a first step in this direction, a detailed spectroscopic study of methyltrioxorhenium (MTO) has been undertaken. It is an ideal test molecule as the achiral parent molecule of chiral candidates for a parity violation experiment. For the (187)Re MTO isotopologue, a combined analysis of Fourier transform microwave and infrared spectra as well as ultra-high resolution CO(2) laser absorption spectra enabled the assignment of 28 rotational lines and 71 rovibrational lines, some of them with a resolved hyperfine structure. A set of spectroscopic parameters in the ground and first excited state, including hyperfine structure constants, was obtained for the ν(as) antisymmetric Re=O stretching mode of this molecule. This result validates the experimental approach to be followed once a chiral derivative of MTO is synthesized, and shows the benefit of the combination of several spectroscopic techniques in different spectral regions, with different set-ups and resolutions. The first high resolution spectra of jet-cooled MTO, obtained on a set-up being developed for the observation of molecular parity violation, are shown, which constitutes a major step towards the targeted objective. 相似文献
62.
The hyperfine structure of methyl formate was recorded in the 2-20 GHz range. A molecular beam coupled to a Fourier transform microwave spectrometer having an instrumental resolution of 0.46 kHz and limited by a Doppler width of a few kHz was used. A-type lines were found split by the magnetic hyperfine coupling while no splittings were observed for E-type lines. Symmetry considerations were used to account for the internal rotation of the methyl top and to derive effective hyperfine coupling Hamiltonians. Neglecting the spin-rotation magnetic coupling, the vanishing splittings of the E-type lines could be understood and analyses of the hyperfine patterns of the A-type lines were performed. The results are consistent with a hyperfine structure dominated by the magnetic spin-spin coupling due to the three hydrogen atoms of the methyl group. 相似文献
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64.
We propose a simple model of first impression bias (FIB), where agents tend to ignore features which contradict their initial view. We consider a population of agents which are all in contact with a media, communicating randomly chosen features of an object. In some cases, we observe on simulations that FIB is significantly more frequent when the agents interact with each other than when they are only in contact with the media. We design an analytical aggregated model of the global agent‐based model behavior, which helps to explain the higher number of FIB due to the interactions. © 2009 Wiley Periodicals, Inc. Complexity, 2010 相似文献
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66.
Rotation barriers around the metal—pyridine bond of various macrocyclic complexes of cobalt(III), rhodium(III), zinc(II) and magnesium(II) have been studied using the 13C longitudinal relaxation times, T1, of the carbon atoms of pyridine and the macrocycle. The data have been rationalized on the basis of steric and electronic factors. The influence of π back-donation on the rates of rotation around the axial Co? N and Rh? N bonds is discussed. The agreement found between the conclusions drawn from this study and X-ray data reported for complexes of identical or closely related structure demonstrates the validity of this method. 相似文献
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68.
A spectrum of HSiF(3) has been recorded at room temperature with a gas pressure of 20-50 Torr in the near-infrared region. A laser photoacoustic spectrometer consisting of a longitudinal resonant cell coupled to a titanium:sapphire ring laser was employed. The 5nu(1) and 6nu(1) overtone bands of H(28)SiF(3) associated with the Si-H stretching have been observed at high resolution (3 x 10(-2) cm(-1)) in the regions 10 900-10 960 and 12 875-12 925 cm(-1), respectively. About 450 lines of the 5nu(1)-0 band have been assigned (J = 45, K = 3p = 18). Within each J cluster of the P and R branches, the K structure has been deconvoluted. A set of parameters characterizing the upper vibration-rotation structure has been obtained. Perturbations have been evidenced for K = 9 and 15. The characterization of the perturbed 6nu(1)-0 band was limited to J = 38, and effective parameters have been determined with no detailed information on the K structure. Most perturbations are supposedly due to the cubic anharmonic constant φ(144) linking nnu(1) to (n - 1)nu(1) + 2nu(4) (n = 5, 6) and to their accompanying interacting rovibrational states. Copyright 2000 Academic Press. 相似文献
69.
Aviles-Moreno JR Demaison J Huet TR 《Journal of the American Chemical Society》2006,128(32):10467-10473
Conformational flexibility in the smallest hydrated sugar, the glycolaldehyde-water complex, has been investigated in the gas phase by means of a combination of a microwave Fourier transform spectroscopy experiment in a supersonic molecular beam and ab initio quantum chemistry calculations. The water molecule inserts into glycolaldehyde using H-bonding selectivity: the two lowest energy conformations are stabilized by two intermolecular hydrogen bonds, and the next two by one intra- plus one intermolecular hydrogen bond. A dynamical flexibility associated with the two lowest energy conformations has been experimentally observed and accurately modeled with a two-dimensional potential energy surface involving the hydroxyl group and the free OH water group coordinates. The conclusions drawn from the role played in the conformational flexibility by the hydroxyl and carbonyl groups are extended to other carbohydrates and biomolecules. 相似文献
70.
Huiban M Huet A Barré L Sobrio F Fouquet E Perrio C 《Chemical communications (Cambridge, England)》2006,(1):97-99
The 11C-monomethylstannate prepared from [11C]-methyl iodide and Lappert's stannylene, was subject to a palladium-mediated cross-coupling reaction with an aryl halide under ligand-free conditions, to afford easily purified 11C-methyl(hetero)arenes in high radiochemical yields. 相似文献