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1.
The structure and rotational barrier for the mesityl-silicon bond of 2,2-dimesityl-1,1,1,3,3,3-hexamethyltrisilane have been investigated by 1H- and 13C-variable temperature nuclear magnetic resonance (NMR) as well as by density functional theory structural calculations. The calculations show that the lowest energy structure has C2 symmetry with nonequivalent ortho methyl groups, consistent with the crystal structure and solution NMR. The nonequivalent ortho methyl groups exchange through a Cs transition state with a calculated relative free energy of 11.0 kcal mol−1. The barrier for this rotation found by dynamic NMR is 13.4 ± 0.2 kcal mol−1 at 298 K. 相似文献
2.
分析学生对二氧化碳的3个典型学科认知障碍,以“二氧化碳的捕捉”为情境,通过“尝试捕捉二氧化碳”“谁在捕捉二氧化碳”“捕捉背后的原理”等3个主要环节,实现对学科认知障碍的突破,展示了一种新的中考复习教学思路。 相似文献
3.
We develop an effective numerical method of studying large-time properties of reversible reaction-diffusion systems of type
A + B ↔ C with initially separated reactants. Using it we find that there are three types of asymptotic reaction zones. In particular
we show that the reaction rate can be locally negative and concentrations of species A and B can be nonmonotonic functions
of the space coordinate x, locally significantly exceeding their initial values.
Received 6 June 2002 / Received in final form 20 January 2003 Published online 7 May 2003 相似文献
4.
Büttiker and Landauer studied scattering off an oscillating rectangular barrier in order to shed light on the time aspects of tunneling. The expression for the traversal time resulting from this study is controversial. In addition, doubts have recently been expressed on technical aspects of their work. In an attempt to clarify these issues, we investigate a generalization of their model to arbitrary oscillating barriers,V(x, t)=V
0(x)+V
1(x)cos t. In the process, we confirm that Büttiker and Landauer's work is technically sound. However, we show, by several examples, that no direct general relation exists between the characteristic frequency of an oscillating barrier and the duration of the tunneling process. For a wide range of realistic parameters this characteristic frequency does not even exist.This paper is dedicated to E. G. D. Cohen. 相似文献
5.
J. Lewin 《Journal of Optimization Theory and Applications》1986,49(3):411-430
A pursuerP, whose speed is bounded by 1, wants to get closer to an evaderE, whose speed is bounded by >1.P wants to reduce his distancePE fromE below the capture radius . Both players are confined to a circular arena. This problem is equivalent to a problem discussed by Flynn, who characterized and gave numerical bounds to the least upper boundd* on the values ofPE thatE can maintain. He used direct methods and did not use Isaacs' theory.We solve our problem relying on the theory of singular surfaces in differential games. We construct and investigate barriers of the game of kind, and we replace Flynn's bounds ond* by analytical (exact) values for various speeds .The support of the TW Department of THT, Enschede, Holland, is gratefully acknowledged. 相似文献
6.
The molecular and electronic structure of the ground state of peroxyacetyl nitrate (PAN) was calculated by the unrestricted
Hartree-Fock-Roothaan method with the use of the standard 3–21G and 6–31G basis set. The potential curve of the internal rotation
about the peroxide bond of PAN was calculated with the 6–31G basis set. The curve contains two maxima. The ground state of
PAN is characterized by a structure in which groups of atoms adjacent to the peroxide bond lie in planes that are perpendicular
to each other (the dihedral angle ϱ(COON) is 89.9°). The calculated barriers to rotation are 19.6 and 66.8 kJ mol−1.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 600–604, April, 1998. 相似文献
7.
Synthesis and inversion barriers of undeca- and dodeca-substituted saddle shaped porphyrin complexes
Synthesis and barriers to inversion of a series of highly saddle shaped complexes are reported. The ΔG≠ has decreased by 8 kJ mol−1 at 243 K when the meso phenyl groups are replaced by bulkier 2,6-dichlorophenyl groups, and by 17 kJ mol−1 when one of the peripheral ethyl groups is removed. 相似文献
8.
V. G. Avakyan L. E. Gusel’nikov S. L. Gusel’nikov V. F. Sidorkin 《Russian Chemical Bulletin》2005,54(9):2013-2022
The effect of the nature of substituents at sp2-hybridized silicon atom in the R2Si=CH2 (R = SiH3, H, Me, OH, Cl, F) molecules on the structure and energy characteristics of complexes of these molecules with ammonia, trimethylamine,
and tetrahydrofuran was studied by the ab initio (MP4/6-311G(d)//MP2/6-31G(d)+ZPE) method. As the electronegativity, χ, of the substituent R increases, the coordination bond
energies, D(Si← N(O)), increase from 4.7 to 25.9 kcal mol−1 for the complexes of R2Si=CH2 with NH3, from 10.6 to 37.1 kcal mol−1 for the complexes with Me3N, and from 5.0 to 22.2 kcal mol−1 for the complexes with THF. The n-donor ability changes as follows: THF ≤ NH3 < Me3N. The calculated barrier to hindered internal rotation about the silicon—carbon double bond was used as a measure of the
Si=C π-bond energy. As χ increases, the rotational barriers decrease from 18.9 to 5.2 kcal mol−1 for the complexes with NH3 and from 16.9 to 5.7 kcal mol−1 for the complexes with Me3N. The lowering of rotational barriers occurs in parallel to the decrease in D
π(Si=C) we have established earlier for free silenes. On the average, the D
π(Si=C) energy decreases by ∼25 kcal mol−1 for NH3· R2Si=CH2 and Me3N·R2Si=CH2. The D(Si←N) values for the R2Si=CH2· 2Me3N complexes are 11.4 (R = H) and 24.3 kcal mol−1 (R = F). sp2-Hybridized silicon atom can form transannular coordination bonds in 1,1-bis[N-(dimethylamino)acetimidato]silene (6). The open form (I) of molecule 6 is 35.1 and 43.5 kcal mol−1 less stable than the cyclic (II, one transannular Si←N bond) and bicyclic (III, two transannular Si←N bonds) forms of this molecule, respectively. The D(Si←N) energy for structure III was estimated at 21.8 kcal mol−1.
Dedicated to Academician N. S. Zefirov on the occasion of his 70th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1952–1961, September, 2005. 相似文献
9.
ZHAO Xue CHEN De-Zhan WANG Zhen HAO Zhao-Ling 《结构化学》2007,26(8):980-987
5,8-Hihydroxyl-1,4-naphthazarin was taken as a model compound to explore the effect of halogen substitution on intramolecular proton transfer process. Calculations indicate that the substitution in the R2- and R4-positions far away from the active region has much weaker influence on the IPT process than that in the R1-and R3-positions. IPT barriers for substitution in the R1-position are higher than that of parent molecule. However, it is quite reverse for substitution in the R3-position. The IPT process is a proton transfer process coupled with charge separation and coulombic interaction would be dominant during this process. As for naphthazarin, halogen substitution would decrease the quantum yields of O2 but increase those of 1O2. 相似文献
10.
WANG Yan ZENG Xiao-Lan SHEN Sai-Jun 《结构化学》2007,26(7):767-772
The mechanism, catalytic effect and solvent effect of the hetero-Diels-Alder reac- tions between 3-pyridinedithioesters and 1-phenylsulfanylbutadiene have been studied theoretically using density functional theory (DFT) at the B3LYP/6-31G(d) level. The results show that all of these reactions proceed in a concerted but asynchronous way. In some reactions the formation of C-S bond is prior to that of C-C bond and the opposite results are found in other reactions. The BF3 catalyst may lower the activation barriers by changing the energies of LUMO for 3-pyridine- dithioester. THF solvent has trivial influence on the potential energy surface of these reactions. With the BF3-catalyzed reactions, regioselectivity and stereoselectivity observed experimentally were predicted correctly by calculations and these results originate probably from C-H···F interaction in two transition states. 相似文献