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131.
The dimers [Cu(2)(dppm)(2)(CN-t-Bu)(3)](BF(4))(2) and [Ag(2)(dppm)(2)(CN-t-Bu)(2)](X)(2) (X(-) = BF(4)(-), ClO(4)(-)) and the coordination polymers [[M(diphos)(CN-t-Bu)(2)]BF(4)](n) (M = Cu, Ag; diphos = bis(diphenylphosphino)butane (dppb), bis(diphenylphosphino)pentane (dpppen), bis(diphenylphosphino)hexane (dpph)), [[Ag(2)(dppb)(3)(CN-t-Bu)(2)](BF(4))(2)](n), and [[Ag(dpppen)(CN-t-Bu)]BF(4)](n) have been synthesized and fully characterized as model materials for the mixed bridging ligand polymers which exhibit the general formula [[M(diphos)(dmb)]BF(4)](n) (M = Cu, Ag; dmb = 1,8-diisocyano-p-menthane) and [[Ag(dppm)(dmb)]ClO(4)](n). The identity of four polymers ([[Ag(dppb)(CN-t-Bu)(x)]BF(4)](n) (x = 1, 2), [[Ag(2)(dppb)(3)(CN-t-Bu)(2)](BF(4))(2)](n), [[Ag(dppm)(dmb)]ClO(4)](n)) and the two dimers has been confirmed by X-ray crystallography. The structure of [[Ag(dppm)(dmb)]ClO(4)](n) exhibits an unprecedented 1-D chain of the type "[Ag(dmb)(2)Ag(dppm)(2)(2+)](n)", where d(Ag(.)Ag) values between tetrahedral Ag atoms are 4.028(1) and 9.609(1) A for the dppm and dmb bridged units, respectively. The [[Ag(dppb)(CN-t-Bu)(x)]BF(4)](n) polymers (x = 1, 2) form zigzag chains in which the Ag atoms are tri- and tetracoordinated, respectively. The [[Ag(2)(dppb)(3)(CN-t-Bu)(2)](BF(4))(2)](n) polymer, which is produced from the rearrangement of [[Ag(dppb)(CN-t-Bu)(2)]BF(4)](n), forms a 2-D structure described as a "honeycomb" pattern, where large [Ag(dppb)(+)](6) macrocycles each hosting two counterions and two acetonitrile guest molecules are observed. Properties such as glass transition temperature, morphology, thermal decomposition, and luminescence in the solid state at 293 K are reported. The luminescence bands exhibit maxima between 475 and 500 nm with emission lifetimes ranging between 6 and 55 micros. These emissions are assigned to a metal-to-ligand charge transfer (MLCT) of the type M(I) --> pi(NC)/pi(PPh(2)). 相似文献
132.
Fournier I Marinach C Tabet JC Bolbach G 《Journal of the American Society for Mass Spectrometry》2003,14(8):893-899
Irradiation effects at low and high laser fluence on 2,5-dihydroxybenzoic acid large crystals were investigated. Contrary to what was observed for matrices as cinnamic acid derivatives, no chemical degradation of matrix is evidenced and continuous ablation as well as ion production resulted of extended irradiation in all the fluence range corresponding to classical matrix-assisted laser desorption /ionization. Ripples are formed on the base of the crater for a limited number of laser shots under moderate fluence. For extended irradiation, conical shape craters are formed with the axis of the crater oriented along the incident direction of the laser beam. A study of the craters showed that ablation through the ablated volume slowly varied with the laser fluence when a strong increase of ion production (matrix and analyte) was recorded. Ablation volume was found to vary non-linearly with the number of laser shots. On a same spot, the ablated volume and the ion production were measured as a function of the laser energy. With an increasing laser energy (or fluence), the ablated volume slowly increases when the ion production strongly increases. This gives evidence of a decoupling between ablation and ionization. Interaction of the plume with the incoming beam is thus probable. 相似文献
133.
With Li+ or TBA+ as counter ion the electrodimerization of phenylpent-2-en-3-one occurs by a 0.2 F initiation. This reaction is regio- and stereospecific with Li+, the radical autocatalytic reaction gave 100% yield of a new dimer. If TBA+ is used the primary step is an ion-substrate reaction giving two isomers in equal proportion. All reaction products were structurally determined by 2D-NMR (SECSY or COSY and NOESY sequence). 相似文献
134.
Fournier F Zheng W Carrez S Dubost H Bourguignon B 《The Journal of chemical physics》2004,121(10):4839-4847
Interaction of CO adsorbed on Pt(111) with electrons and phonons is studied experimentally by means of a pump-probe experiment where CO is probed by IR + visible sum frequency generation under a pump laser intensity that allows photodesorption. Vibrational spectra of CO internal stretch are obtained as a function of pump-probe delay. A two-temperature and anharmonic coupling model is used to extract from the spectra the real time variations of CO peak frequency and dephasing time. The main conclusions are the following: (i) The CO stretch is perturbed by two low-frequency modes, assigned to frustrated rotation and frustrated translation. (ii) The frustrated rotation is directly coupled to electrons photoexcited in Pt(111) by the pump laser. (iii) There is no evidence of Pt-CO stretch excitation in the spectra. The implications for the photodesorption dynamics are discussed. 相似文献
135.
136.
We tested the efficacy of three empirical correction schemes on atomization energies calculated by the following theories: Kohn–Sham density functional theory (KS-DFT) with local spin density approximation (LSDA), two KS-DFT gradient-corrected methods, one hybrid Hartree–Fock/KS-DFT method similar to B3LYP, and the ab initio extrapolation procedures G1 and G2. Empirical corrections improved the LSDA results greatly, while the other theories were improved slightly or not at all. The best procedure for correcting LSDA atomization energies brings the mean absolute deviation from experiment from 38.3 to 4.0 kcal/mol on a subset of 44 molecules in the G1 dataset that were not used in deriving the empirical parameters. This corrected LSDA is interesting for three reasons: it could be a useful computational tool in some cases, it implies that the LSDA itself gives accurate energies for reactions where atomic coordinations stay unchanged, and it gives insight into the search of better functionals. 相似文献
137.
DR.G. Domairry A. Mohsenzadeh M. Famouri 《Communications in Nonlinear Science & Numerical Simulation》2009,14(1):85-95
In this paper Jeffery–Hamel flow has been studied and its nonlinear ordinary differential equation has been solved through homotopy analysis method (HAM). The obtained solution in comparison with the numerical ones represents a remarkable accuracy. The results also indicate that HAM can provide us with a convenient way to control and adjust the convergence region. 相似文献
138.
It is very important to understand how the heat
diffuses in the case of nano objects and of layered structures. We will
demonstrate that the lateral diffusion could be very different in the case
of a good conductor layer deposited on a bad one and for the reverse (bad
one on good substrate). Moreover, we will show how a thermoreflectance
experiment can reveal both the thermal conductivity and the thermal
diffusivity of thin layers deposited on substrates. 相似文献
139.
We identify a class of composite membranes: fluid bilayers coupled to an elastic meshwork that are such that the meshwork's energy is a function F(el)[A(xi)] not of the real microscopic membrane area A, but of a smoothed membrane's area A(xi), which corresponds to the area of the membrane coarse grained at the mesh size xi. We show that the meshwork modifies the membrane tension sigma both below and above the scale xi, inducing a steep crossover of amplitude deltasigma=dF(el)/dA(xi). The predictions of our model account for the fluctuation spectrum of red blood cell membranes coupled to their cytoskeleton. Our results indicate that the cytoskeleton might be under extensional stress, which would provide a means to regulate available membrane areas. We also predict an observable tension jump for membranes decorated with polymer "brushes." 相似文献
140.