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41.
Diane C. Rawlings Ernest R. Davidson Martin Gouterman 《International journal of quantum chemistry》1984,26(2):237-250
A new minimum basis set was developed for use in computing excitation energies of large molecules. It is particularly suited to calculating ionization potentials and Rydberg transitions. Pyrrole excitation energies and oscillator strengths calculated with this basis set are compared to larger basis set ab initio and semiempirical results. The 6-eV band in the experimental spectrum is predicted to be the result of three Rydberg absorptions, with no underlying (π, π*) absorption. The calculations also provide an explanation for the observed N? H stretch in the 6-eV region. 相似文献
42.
Rates of volatilisation and chain scission have been measured in the thermal degradation, photodegradation in solution, photodegradation in thin films and photothermal degradation of poly(methyl methacrylate) and a series of copolymers of methyl methacrylate with maleic anhydride. In each case the rate of volatilisation is depressed by the maleic anhydride units. On the other hand, rates of chain scission are accelerated by maleic anhydride except in the case of photothermal degradation. These results are discussed from a mechanistic point of view. 相似文献
43.
Stephen R. Langhoff Stephen T. Elbert Ernest R. Davidson 《International journal of quantum chemistry》1973,7(5):999-1019
The electron spin dipole-dipole contribution to the zero field splitting has been evaluated for the 3A2 (n → π*) and 3A1 (π → π*) states of formaldehyde using a CI wave function constructed from contracted Gaussian-lobe functions. The values D = 0.539 cm?1 and E = 0.031 cm?1 were obtained for the 3A2(n → π*) state and D = ?0.588 cm?1 and E = 0.058 cm?1 were obtained for the 3A1 (π → π*) state using the CI wave function constructed from SCF orbitals of the respective parent configurations. An analysis of the effect of CI on the parameters is given for the 3A2 (n n → π*) state of formaldehyde and the 3B1 ground state of methylene. Numerical results are given which show that internally consistent self-consistent field orbitals (ICSCF ) are superior to canonical SCF orbitals as a starting point for a CI calculation. Our CI wave function for the 1A1 ground state gave an energy of ?114.13658 hartrees which is significantly lower than any previously reported energy calculation. This wave function gives a dipole moment of 2.22 Debye (C+O?) in good agreement with the experimental value of 2.33 ± 0.02 Debye. 相似文献
44.
45.
A numerical model of the negative DC corona plasma along a thin wire in dry air is presented. The electron number density and electric field are determined from solution of the one-dimensional coupled continuity equations of charge carriers and Maxwell's equation. The electron kinetic energy distribution is determined from the spatially homogeneous Boltzmann equation. A parametric study is conducted to examine the effects of linear current density (0.1–100 A per cm of wire length), wire radius (10–1000 m), and air temperature (293–800 K) on the distribution of electrons and the Townsend second ionization coefficient. The results are compared to those previously determined for the positive corona discharge. In the negative corona, energetic electrons are present beyond the ionization boundary and the number of electrons is an order of magnitude greater than in the positive corona. The number of electrons increases with increasing gas temperature. The electron energy distribution does not depend on discharge polarity. 相似文献
46.
47.
W. Davidson 《General Relativity and Gravitation》1992,24(2):179-185
Non-stationary cylindrically symmetric one-parameter solutions to Einstein's equations are given for a perfect fluid. There is a time singularity (t=0) at which the pressurep and density are equal to + throughout the radial coordinate range 0 r < , but the solutions are well behaved fort > 0,p and decreasing steadily to zero asr increases through the range 0r<, or as t increases through the range 0<t<. The motion is irrotational with shear, expansion and acceleration. The family of solutions, of Petrov type I, are generally spatially inhomogeneous, of class B(ii), having two spacelike Killing vectors which are mutually orthogonal and hypersurface orthogonal, associated with an orthogonally transitive groupG
2. The particular members for which there are equations of statep=/3 andp= are specially considered. 相似文献
48.
Sabatino Nacson Alex. G. Harrison William R. Davidson 《Journal of mass spectrometry : JMS》1986,21(6):317-319
The collision-induced dissociation (CID) mass spectra of protonated cocaine and protonated heroin have been measured using a triple quadrupole mass spectrometer at 50 eV ion/neutral collision energy for protonated molecules prepared by different protonating agents. The CID mass spectra of protonated cocaine using H+(H2O)n, H+(NH3)n and H+((CH3)2NH)n as protonating agents are essentially identical and it is concluded that, regardless of the initial site of protonation, the fragmentation reactions occurring on collisional activation are identical. By contrast, protonated heorin prepared with H+(H2O)n and H+(NH3)n as protonating agents show substantial differences. That formed by reaction of H+(H2O)n shows a much more abundant peak corresponding to loss of CH3CO2H. From a comparison with model compounds, and from a consideration of the three-dimensional structure of heroin, it is concluded that with H+(H2O)n as protonating agent significant protonation occurs at the acetate group attached to the alicyclic ring, leading to acetic acid loss on collisional activation, but that reaction of H+(NH3)n leads to protonation at the nitrogen function. The proton attached to nitrogen cannot interact with the acetate group and, consequently, the probability of loss of acetic acid on collislional activation is greatly reduced. 相似文献
49.
α-Oxo-carboxylic acids undergo photo-oxidative decarboxylation from both C-1 and C-2 positions, and reaction does not involve singlet oxygen: a mechanism involving an electron transfer reaction is postulated. 相似文献
50.
Lam WH Gaspar PP Hrovat DA Trieber DA Davidson ER Borden WT 《Journal of the American Chemical Society》2005,127(27):9886-9894
CASSCF, CASPT2, CCSD(T), and (U)B3LYP electronic structure calculations have been performed in order to investigate the thermal fragmentation of P-phenylphosphirane (1) to phenylphosphinidene (PhP) and ethylene. The calculations show that generation of triplet PhP via a stepwise pathway is 21 kcal mol(-1) less endothermic and has a 12 kcal mol(-1) lower barrier height than concerted fragmentation of 1 to give singlet PhP. The formation of singlet PhP via a concerted pathway is predicted to be stereospecific, whereas formation of triplet PhP is predicted to occur with complete loss of stereochemistry. However, calculations on fragmentation of anti-cis-2,3-dimethyl-P-mesitylphosphirane (cis-1Me) to triplet mesitylphosphinidene (MesP) indicate that this reaction should be more stereospecific, in agreement with the experimental results of Li and Gaspar. Nevertheless, with a predicted free energy of activation of 42 kcal mol(-1), the formation of MesP from cis-1Me is not likely to have occurred in an uncatalyzed reaction at the temperatures at which this phosphirane has been pyrolyzed. 相似文献