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51.
52.
Yury Yu. Rusakov Leonid B. Krivdin Valentina M. Nosova Alexander V. Kisin Valentin G. Lakhtin 《Magnetic resonance in chemistry : MRC》2012,50(10):665-671
The calculations of geminal and vicinal 29Si–1H spin–spin coupling constants across double bond in 15 alkenylmethylsilanes and alkenylchlorosilanes were carried out at the second‐order polarization propagator approach level in a good agreement with experiment. Two structural trends, namely, (i) the geometry of the coupling pathway and (ii) the effect of the electrowithdrawing substituent, have been interpreted in terms of the natural J‐coupling analysis within the framework of the natural bond orbital approach. Thus, the marked difference between cisoidal and transoidal 29Si–1H spin–spin coupling constants across double bond was accounted for the delocalization contributions including bonding and antibonding Si–C and C–H orbitals, whereas the chlorine effect was explained in terms of the steric contributions including bonding Si–Cl orbitals. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
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Normal halogen dependence of 13C NMR chemical shifts of halogenomethanes revisited at the four‐component relativistic level
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Dmitry O. Samultsev Yury Yu. Rusakov Leonid B. Krivdin 《Magnetic resonance in chemistry : MRC》2016,54(10):787-792
The ‘Normal Halogen Dependence’ of 13C NMR chemical shifts in the series of halogenomethanes is revisited at the four‐component relativistic level. Calculations of 13C NMR chemical shifts of 70 halogenomethanes have been carried out at the density functional theory (DFT) and MP2 levels with taking into account relativistic effects using the four‐component relativistic theory of Dirac‐Coulomb within the different computational methods (4RPA, 4OPW91) and hybrid computational schemes (MP2 + 4RPA, MP2 + 4OPW91). The most efficient computational protocols are derived for practical purposes. Relativistic shielding effect reaches as much as several hundreds of ppm for heavy halogenomethanes, and to account for this effect in comparison with experiment at the qualitative level, relativistic Dyall's basis sets of triple‐zeta quality or higher are to be used within the framework of the four‐component relativistic theory taking into account solvent effects. Relativistic geometrical optimization (as compared with the non‐relativistic level) is essential for the molecules containing at least two iodines at one carbon atom. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
55.
Yury Yu. Rusakov Leonid B. Krivdin Maxim V. Penzik Vladimir A. Potapov Svetlana V. Amosova 《Magnetic resonance in chemistry : MRC》2012,50(10):653-658
Stereochemical structure of nine Z‐2‐(vinylsulfanyl)ethenylselanyl organyl sulfides has been investigated by means of experimental measurements and second‐order polarization propagator approach calculations of their 1H–1H, 13C–1H, and 77Se–1H spin–spin coupling constants together with a theoretical conformational analysis performed at the MP2/6‐311G** level. All nine compounds were shown to adopt the preferable skewed s‐cis conformation of their terminal vinylsulfanyl group, whereas the favorable rotational conformations with respect to the internal rotations around the C–S and C–Se bonds of the internal ethenyl group are both skewed s‐trans. Stereochemical trends of 77Se–1H spin–spin coupling constants originating in the geometry of their coupling pathways and the selenium lone pair effect were rationalized in terms of the natural J‐coupling analysis within the framework of the natural bond orbital approach. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
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A theoretical study of geminal and vicinal 77Se‐1 H coupling constants in the benchmark dimethyl and diethyl selenides has been performed at the SOPPA level followed by the NJC analysis within the NBO approach to reveal their stereochemical behavior in respect with the three main structural factors, namely, (i) the dihedral angle dependences, (ii) the bond angle dependences and (iii) the lone pair effects. It has been demonstrated that both geminal and vicinal couplings provide a unique stereospecificity in respect with the orientational lone pair effect together with the geometry of a coupling pathway, which is of prime importance for the stereochemical studies of organoselenium compounds. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
58.
We reduce the solution of contact problems in the interaction of rigid bodies (dies) with thin-walled elements (one-dimensional
problems) to Volterra integral equations. We study the effect of the model describing the stress-strain state of plates on
the type of integral equations and the structure of their solutions. It is shown that taking account of reducing turns the
problem into a Volterra integral equation of second kind, which has a unique solution that is continuous and agrees quite
well with the results obtained from the three-dimensional theory. In the case of a theory of Timoshenko type the problem is
reduced to a Volterra three-dimensional theory. In the case of a theory of Timoshenko type the problem is reduced to a Volterra
integral equation of first kind that has a unique continuous solution; but for dies without corners the Herz condition does
not hold (p(a) ≠ 0), and the contact pressure assumes its maximal value at the end of the zone of contact. For thin-walled
elements, whose state can be described by the classical Kirchhoff-Love theory, the integral equation of the problem (a Volterra
equation of first kind) has a solution in the class of distributions. The contact pressure is reduced to concentrated reactions
at the extreme points of the contact zone. We give a comparative analysis of the solutions in all the cases just listed (forces,
normal displacements, contact pressures). Three figures, 1 table. Bibliography: 5 titles.
Translated fromTeoreticheskaya i Prikladnaya Mekhanika, No. 27, 1997, pp. 96–103. Original article submitted March 15, 1997. 相似文献
59.
Wågberg T Johnels D Peera A Hedenström M Schulga YM Tsybin YO Purcell JM Marshall AG Noreus D Sato T Talyzin AV 《Organic letters》2005,7(25):5557-5560
[chemical structure: see text]. C60H18 has been produced by hydrogenation of C60 at 100 bar H2 pressure and 673 K for 10 h. We have investigated the crude material without any purification by use of 1H NMR, 13C NMR, and IR spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry. We show that the crude material consists of 95% of the C3v isomer of C60H18. 相似文献
60.
We show both theoretically and experimentally that an electromagnetic wave can be totally absorbed by an overdense plasma when a subwavelength diffraction grating is placed in front of the plasma surface. The absorption is due to dissipation of surface plasma waves (plasmons polaritons) that have been resonantly excited by the evanescent component of the diffracted electromagnetic wave. The developed theoretical model allows one to determine the conditions for the total absorption. 相似文献