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As ab initio electronic structure calculations become more accurate, inherent sources of error in classical transition state theory such as barrier recrossing and tunneling may become major sources of error in calculating rate constants. This paper introduces a general method for diabatically constructing the transverse eigensystem of a reaction path Hamiltonian in systems with many degenerate transverse frequencies. The diabatically constructed reaction path Hamiltonian yields smoothly varying coupling constants that, in turn, facilitate reactive flux calculations. As an example we compute the dynamically corrected rate constant for the chair to boat interconversion of cyclohexane, a system with 48 degrees of freedom and a number of degenerate frequencies. The transmission coefficients obtained from the reactive flux simulations agree with previous results that have been calculated using an empirical potential. Furthermore, the calculated rate constants agree with experimental values. Comparison to variational transition state theory shows that, despite finding the true bottleneck along the reaction pathway, variational transition state theory only accounts for half of the rate constant reduction due to recrossing trajectories. 相似文献
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Desmet G Vervoort N Clicq D Huau A Gzil P Baron GV 《Journal of chromatography. A》2002,948(1-2):19-34
It is only by developing specially designed injection and detection systems that shear-driven chromatography can become a viable alternative to HPLC. In the present paper, a dedicated zero dead-volume injection procedure is presented with which sample volumes can be injected reproducibly in the required picoliter range. In addition, a transversal detection groove system is designed which should allow to perform on-line UV-VIS absorption measurements with path lengths in the millimeter range, with an acceptable theoretical plate loss (only 20% in a 5 cm long channel) and acting as a nearly perfect wave guide. 相似文献
5.
Studies on the capacity of Pr in uitro to photoconvert to the long wavelength in uioo-like Pfr form were performed with extracts from 10 species. Red irradiation, immediately after extraction of crude extracts from 9 species, photoconverted Pr to long-wavelength Pfr with an absorbance maximum around 735 nm. Red irradiation of soybean extracts, however, photoconverted Pr to short-wavelength Pfr, with an absorbance maximum at 725 nm. Red irradiation given later than 1.5-2 h after extraction, to extracts of oats, pea, cucumber, radish, sunflower and soybean, photoconverted Pr to a short-wavelength Pfr species with an absorbance maximum around 725 nm. In crude extracts of barley, corn, wheat and zucchini, red irradiation, even after a long dark-incubation period at 4°C of up to 48 h, photoconverted Pr to long-wavelength Pfr with an absorbance maximum around 735 nm. After incubation at 25°C for 3 h, however, Pr from barley also photoconverted to the short-wavelength form. It is suggested that in the group exemplified by oats, Pr rapidly undergoes an alteration following extraction, which results in the loss of the capacity of Pr to photoconvert to long-wavelength Pfr. In contrast, in extracts from the group exemplified by barley, Pr is much more stable and retains the capacity to photoconvert to long-wavelength Pfr for much longer periods. 相似文献
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The microwave spectrum of the main isotopic species of cyclopentadienone has been measured and assigned. The rotational constants imply an essentially planar geometry and that the ring is rather “fatter” than the analogous ring in fulvene.The dipole moment, derived from Stark-effect measurements, is 10.4 × 10?30 C m (3.13 D). A vibrational satel- lite spectrum, which, from its inertial defect, corresponds to an out-of-plane vibration has also been assigned.The life time of cyclopentadienone under our spectroscopic conditions is approximately 15 sec. 相似文献
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Interpolation methods such as the nudged elastic band and string methods are widely used for calculating minimum energy pathways and transition states for chemical reactions. Both methods require an initial guess for the reaction pathway. A poorly chosen initial guess can cause slow convergence, convergence to an incorrect pathway, or even failed electronic structure force calculations along the guessed pathway. This paper presents a growing string method that can find minimum energy pathways and transition states without the requirement of an initial guess for the pathway. The growing string begins as two string fragments, one associated with the reactants and the other with the products. Each string fragment is grown separately until the fragments converge. Once the two fragments join, the full string moves toward the minimum energy pathway according to the algorithm for the string method. This paper compares the growing string method to the string method and to the nudged elastic band method using the alanine dipeptide rearrangement as an example. In this example, for which the linearly interpolated guess is far from the minimum energy pathway, the growing string method finds the saddle point with significantly fewer electronic structure force calculations than the string method or the nudged elastic band method. 相似文献
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The microwave spectrum of N2D4 has been observed and analyzed. Based on five low-J rotational transitions the effective rotational constants are: A = 74712.9 ± 1.9 MHz, B = 18500.42 ± 0.46 MHz, and C = 18439.91 ± 0.46 MHz. The quadrupole coupling constants of the 14N nuclei are Xaa = 4.23 ± 0.04 MHz, Xbb = 1.98 ± 0.05 MHz, and Xcc = ?2.25 ± 0.05 MHz. Using the observed ground state inversion splittings for N2D4 and N2H4 the barrier to inversion of a single amino group is computed to be 5.00 kcal mol?1. 相似文献
10.
Koji Yoshida Nobutaka Yamamoto Shinya Hosokawa Alfred Q.R. Baron Toshio Yamaguchi 《Chemical physics letters》2007,440(4-6):210-214
Inelastic X-ray scattering experiments have been performed on methanol as a function of density from ambient to the supercritical state. Positive dispersion of the sound velocity, as compared to the hydrodynamic values, is 50% in the ambient condition and decreases to zero at 0.50 g cm−3 over the momentum transfer Q = 1–10 nm−1 with lowering density; however, it increases again with a further decrease in density down to 0.20 g cm−3in the supercritical state only in the Q-range above 5 nm−1. These results have been interpreted as the formation of small oligomers in the low-density supercritical methanol. 相似文献