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51.
Treatment of alpha,omega-dithiols HS(CH(2))(n)()SH, n = 4 or 5, with tris[(triphenylphosphine)aurio]oxonium tetrafluoroborate affords the corresponding S,S,S',S'-tetrakis[(triphenylphosphine)aurio]-alpha,omega-alkanediylbis(sulfonium) bis(tetrafluoroborates) of the type {[(Ph(3)P)Au](2)S(CH(2))(n)()S[Au(PPh(3))](2)}(2+)2BF(4)(-). The crystal structure of the species with n = 5 has been determined by single crystal X-ray diffraction studies. In the lattice the unfolded dications are linked into chains through short double Au-Au contacts between the terminal bifurcated diauriosulfonium centers. The analogous reactions with (racemic) 1,2-dithioglycerol and 1,2,3-trithioglycerol also give tri- and tetranuclear complexes with a varying distribution of the metal atoms over the chalcogen(ium) centers. As again demonstrated in a single crystal X-ray diffraction study, the dications {HOCH(2)HCS[(Ph(3)P)Au](2)CH(2)S[Au(PPh(3))](2)}(2+) of the dithioglycerol compound form only dimers through auriophilicity-determined pairing of the bifurcated ends, while the open ends are shielded by the dangling hydroxyl group. The trinuclear complex of 1,2-dithioglycerol is fluxional in solution; the crystal structure has not been determined but is expected to be similar to that derived for the analogous dithioglycol complex. The tetranuclear, trithioglycerol-based dications of {[(Ph(3)P)Au]SCH(2)CHS[Au(PPh(3))]CH(2)S[Au(PPh(3))](2)}(+)BF(4)(-) are isolated in the lattice and feature an unsymmetrical complexation, which is an extension of the structure of the trinuclear dithioglycol analogue {(CH(2)S)(2)[Au(PPh(3))](3)}(+) with its strong intramolecular Au-Au contacts. A similar structure is proposed for the monocation {CH(2)(CH(2)S)(2)[Au(PPh(3))](3)}(+) obtained from propane-1,3-dithiol. The structures of these cations are also fluxional in solution, however, as shown by variable-temperature NMR studies. 相似文献
52.
53.
The cross-coupling reaction of pentafluoropyridine with tributyl(vinyl)tin affording 2-vinyltetrafluoropyridine by activation of a carbon-fluorine bond is catalysed by [NiF(2-C5NF4)(PEt3)2]; a similar reaction is observed with 2,3,5,6-tetrafluoropyridine. 相似文献
54.
LeClair P Swagten HJ Kohlhepp JT van De Veerdonk RJ de Jonge WJ 《Physical review letters》2000,84(13):2933-2936
Co/Al2O3/Co magnetic tunnel junctions with an interfacial Cu layer have been investigated with in situ growth characterization and ex situ magnetotransport measurements. Cu interlayers grown on Co give an approximately exponential decay of the tunneling magnetoresistance with xi approximately 0.26 nm while those grown on Al2O3 have a decay length of 0.70 nm. The difference in decay lengths can be explained by different growth morphologies, and in this way clarifies a present disagreement in the literature. For monolayer coverage of Cu, we show that the tunneling spin polarization is suppressed by at least a factor of 2 compared to Co and beyond approximately 5 ML it becomes vanishingly small. 相似文献
55.
Wong KL Chu MS Luce TC Petty CC Politzer PA Prater R Chen L Harvey RW Austin ME Johnson LC La Haye RJ Snider RT 《Physical review letters》2000,85(5):996-999
Experimental evidence is reported of an internal kink instability driven by a new mechanism: barely trapped suprathermal electrons produced by off-axis electron cyclotron heating on the DIII-D tokamak. It occurs in plasmas with an evolving safety factor profile q(r) when q(min) approaches 1. This instability is most active when ECCD is applied on the high field side of the flux surface. It has a bursting behavior with poloidal/toroidal mode number = m/n = 1/1. In positive magnetic shear plasmas, this mode becomes the fishbone instability. This observation can be qualitatively explained by the drift reversal of the barely trapped suprathermal electrons. 相似文献
56.
Focsa C Poclet A Pinchemel B Le Roy RJ Bernath PF 《Journal of Molecular Spectroscopy》2000,203(2):330-338
The A'(1)Pi-X(1)Sigma(+) near-infrared system of CaO was observed for the first time at high resolution using a Fourier transform spectrometer. The A'(1)Pi-X(1)Sigma(+) chemiluminescence was excited in a Ca + N(2)O flame produced in a Broida-type oven. More than 3000 rotational lines, classified into 19 bands involving the A'(1)Pi 0 = v' = 3 and the X(1)Sigma(+) 1 = v" = 7 vibrational levels were measured in the 4000-10 000 cm(-1) region with a precision of 0.005 cm(-1). The X(1)Sigma(+) (v = 0, 1) millimeter-wave and X(1)Sigma(+) (v = 0-3) infrared data available in the literature were merged with our new electronic data in order to obtain improved Dunham constants for the ground state of CaO. Very peculiar perturbations are observed in the higher vibrational levels of the A'(1)Pi state, so the upper levels of transitions with v' = 2 and 3 were represented by term values in our least-squares analysis. The interaction of the A'(1)Pi (v >/= 2) levels with the nearby b(3)Sigma(+) (v-2) levels has been detected. An extended set of A'(1)Pi (v = 0-3) data has been obtained which is suitable for use in a future multistate deperturbation analysis of the a(3)Pi approximately A'(1)Pi approximately b(3)Sigma(+) approximately A(1)Sigma(+) complex of excited states. The new near-infrared spectra of the A'(1)Pi-X(1)Sigma(+) transition of CaO also permits the first direct high-resolution linkage between the orange and green systems and the near-infrared bands. Copyright 2000 Academic Press. 相似文献
57.
Le Roy RJ 《Journal of Molecular Spectroscopy》1999,194(2):189-196
A new way of representing vibration-rotation term values for multiple isotopomers of a given electronic state of a diatomic molecule is presented which resolves problems associated with the way the conventional combined isotopomer expansion represents the atomic mass-dependent JWKB and Born-Oppenheimer breakdown correction terms. Its application to infrared and microwave data for HF and DF yields new Dunham expansion coefficients and Born-Oppenheimer breakdown correction terms for this species. This procedure is implemented in a generally available computer program for fitting to various types of data involving one or several electronic states of multiple isotopomers of a diatomic molecule. Copyright 1999 Academic Press. 相似文献
58.
Two-dimensional (2-d) and axisymmetric consolidation problems are treated with a meshless local Petrov–Galerkin approach. The porous continuum is modeled with Biot’s theory, where the solid displacements and the pore pressure are chosen as unknowns (u-p-formulation). These unknowns are approximated with independent spatial discretizations using the moving least-squares scheme. The method is validated by a comparison with an 1-d analytical solution. Studies with graded material data show that a variable permeability has a strong influence on the consolidation process. The example of a disturbed zone around a borehole shows as well the importance of graded material data. 相似文献
59.
Mikhas'kiv V. V. Sladek J. Sladek V. Stepanyuk A. I. 《International Applied Mechanics》2004,40(6):664-671
The paper addresses the three-dimensional problem on steady-state vibrations of an elastic body consisting of two perfectly joined dissimilar half-spaces with an elliptic mode I crack located in one of the half-spaces normally to the interface. The problem is reduced to a boundary integral equation for the crack opening function. The integration domain of the equation is bounded by the crack domain, and the interaction between the crack and the interface is described by a regular kernel. The equation is solved using the mapping method. Numerical results are obtained for the case where the surfaces of the elliptic crack are subjected to harmonic loading with constant amplitude. The dependences of the stress intensity factors on the wave number are presented for various relationships among the mechanical constants that ensure the absence of near-surface waves 相似文献
60.
Vladimir Sladek Kraiwan Punyain Michal Ilčin Vladimír Lukeš 《International journal of quantum chemistry》2014,114(13):869-878
Optimal structures, electronic and thermodynamic properties of the title complexes are presented. The stability of the hydrogen bonded systems is enhanced by the increasing dipole moments whereas in the halogen bonded systems it is also affected by the atom size in the diatomics. The consecutive addition of fluorine atoms to the pyridine moiety results in the decrease of the interaction energy for both types of the investigated bonds. The substitution on the meta sites in pyridine leads to more stable complexes than the substitution in the ortho position. The role of substitution on electric polarization and electrostatic forces is estimated by the symmetry‐adapted perturbation theory energy decomposition. The predicted Gibbs free energies of the complexes of mono fluorinated pyridines with HCl, HF, and ClF are from ?12 to ?22 kJ mol?1 at 200 K. The possible experimental identification of the complexes with respect to the vibrational modes is discussed. © 2014 Wiley Periodicals, Inc. 相似文献