全文获取类型
收费全文 | 2184篇 |
免费 | 52篇 |
国内免费 | 21篇 |
专业分类
化学 | 1284篇 |
晶体学 | 57篇 |
力学 | 55篇 |
数学 | 303篇 |
物理学 | 558篇 |
出版年
2024年 | 2篇 |
2023年 | 13篇 |
2022年 | 33篇 |
2021年 | 34篇 |
2020年 | 47篇 |
2019年 | 66篇 |
2018年 | 58篇 |
2017年 | 37篇 |
2016年 | 68篇 |
2015年 | 62篇 |
2014年 | 60篇 |
2013年 | 152篇 |
2012年 | 113篇 |
2011年 | 138篇 |
2010年 | 88篇 |
2009年 | 77篇 |
2008年 | 151篇 |
2007年 | 141篇 |
2006年 | 143篇 |
2005年 | 136篇 |
2004年 | 111篇 |
2003年 | 80篇 |
2002年 | 84篇 |
2001年 | 46篇 |
2000年 | 27篇 |
1999年 | 28篇 |
1998年 | 30篇 |
1997年 | 35篇 |
1996年 | 37篇 |
1995年 | 28篇 |
1994年 | 16篇 |
1993年 | 21篇 |
1992年 | 11篇 |
1991年 | 9篇 |
1990年 | 8篇 |
1989年 | 8篇 |
1988年 | 3篇 |
1987年 | 7篇 |
1986年 | 7篇 |
1985年 | 8篇 |
1984年 | 2篇 |
1983年 | 5篇 |
1982年 | 8篇 |
1981年 | 2篇 |
1980年 | 3篇 |
1979年 | 3篇 |
1977年 | 3篇 |
1969年 | 1篇 |
1967年 | 2篇 |
1966年 | 1篇 |
排序方式: 共有2257条查询结果,搜索用时 15 毫秒
61.
de Meijere A Kozhushkov SI Rauch K Schill H Verevkin SP Kümmerlin M Beckhaus HD Rüchardt C Yufit DS 《Journal of the American Chemical Society》2003,125(49):15110-15113
The enthalpies of formation [Delta(g)] of tricyclo[8.2.2.2(4,7)]hexadeca-1(13),2,4(16),5,7(15),10(14),11-heptaene (2, 1,2-dehydro[2.2]paracyclophane or [2.2]paracyclophane-1-ene) and tricyclo[8.2.2.2(4,7)]hexadeca-1(13),2,4(16),5,7(15),8,10(14),11-octaene (3, 1,2,9,10-dehydro[2.2]paracyclophane or [2.2]paracyclophane-1,9-diene) have been determined by measuring their heats of combustion in a microcalorimeter and their heats of sublimation by the transpiration method. Values of the strain energies (SE) [SE(2) = 34.7 kcal mol(-)(1), SE(3) = 42.0 kcal mol(-)(1)] have been derived from the gas-phase heats of formation and are compared with those from MM3 and PM3 calculations and with the corresponding value SE(1) = 30.1 kcal mol(-)(1) for the parent tricyclo[8.2.2.2(4,7)]hexadeca-1(13),4(16),5,7(15),10(14),11-hexaene (1, [2.2]paracyclophane). The higher strain energies of 2 and 3 (by 4.6 and 11.9 kcal mol(-)(1)) are in accord with the well-known increased reactivities of their aromatic rings as a consequence of their increased bending. As revealed by an X-ray crystal structure analysis, the bending in the monoene 2 corresponds to that of 1 and 3 at one of two bridging corners. 相似文献
62.
Erilov DA Bartucci R Guzzi R Shubin AA Maryasov AG Marsh D Dzuba SA Sportelli L 《The journal of physical chemistry. B》2005,109(24):12003-12013
Electron spin-echo envelope modulation (ESEEM) spectroscopy of phospholipids spin-labeled systematically down the sn-2 chain was used to detect the penetration of water (D2O) into bilayer membranes of dipalmitoyl phosphatidylcholine with and without 50 mol % cholesterol. Three-pulse stimulated echoes allow the resolution of two superimposed 2H-ESEEM spectral components of different widths, for spin labels located in the upper part of the lipid chains. Quantum chemical calculations (DFT) and ESEEM simulations assign the broad spectral component to one or two D2O molecules that are directly hydrogen bonded to the N-O group of the spin label. Classical ESEEM simulations establish that the narrow spectral component arises from nonbonded water (D2O) molecules that are free in the hydrocarbon chain region of the bilayer membrane. The amplitudes of the broad 2H-ESEEM spectral component correlate directly with those of the narrow component for spin labels at different positions down the lipid chain, reflecting the local H-bonding equilibria. The D2O-ESEEM amplitudes decrease with position down the chain toward the bilayer center, displaying a sigmoidal dependence on position that is characteristic of transmembrane polarity profiles established by other less direct spin-labeling methods. The midpoint of the sigmoidal profile is shifted toward the membrane center for membranes without cholesterol, relative to those with cholesterol, and the D2O-ESEEM amplitude in the outer regions of the chain is greater in the presence of cholesterol than in its absence. For both membrane types, the D2O amplitude is almost vanishingly small at the bilayer center. The water-penetration profiles reverse correlate with the lipid-chain packing density, as reflected by 1H-ESEEM intensities from protons of the membrane matrix. An analysis of the H-bonding equilibria provides essential information on the binding of water molecules to H-bond acceptors within the hydrophobic interior of membranes. For membranes containing cholesterol, approximately 40% of the nitroxides in the region adjacent to the lipid headgroups are H bonded to water, of which ca. 15% are doubly H bonded. Corresponding H-bonded populations in membranes without cholesterol are ca. 20%, of which ca. 6% are doubly bonded. 相似文献
63.
Sergei N. Yurchenko Jürgen Breidung Walter Thiel 《Theoretical chemistry accounts》2005,114(4-5):333-340
We report a theoretical study of the ground electronic state of BiH3. The potential energy surface (PES) is obtained from coupled cluster CCSD(T) calculations with a large basis set (289 contracted
Gaussian functions). The previously available quartic force field (P4) is extended by adding the dominant quintic and sextic
stretching terms to yield improved potential functions in symmetry coordinates (P6) and Morse-type coordinates (M4). Second-order
rovibrational perturbation calculations on the P4-PES and full variational calculations on the P6-PES and M4-PES yield almost
identical vibrational term values which is rationalized by considering the local mode behavior of BiH3 and the Morse-type character of the M4-PES. The remaining deviations between the computed and observed vibrational term values
must thus be caused by imperfections in the CCSD(T) surface. A refinement of this ab initio surface by a restrained fit to
experimental data allows an essentially perfect reproduction of the observed vibrational term values. Variational calculations
on this refined surface provide predictions for several overtone and combination bands that have not yet been observed.
Dedicated to Hermann Stoll on the occasion of his 60th birthday 相似文献
64.
The present work provides a generalization of Mayer's energy decomposition for the density-functional theory (DFT) case. It is shown that one- and two-atom Hartree-Fock energy components in Mayer's approach can be represented as an action of a one-atom potential V(A) on a one-atom density rho(A) or rho(B). To treat the exchange-correlation term in the DFT energy expression in a similar way, the exchange-correlation energy density per electron is expanded into a linear combination of basis functions. Calculations carried out for a number of density functionals demonstrate that the DFT and Hartree-Fock two-atom energies agree to a reasonable extent with each other. The two-atom energies for strong covalent bonds are within the range of typical bond dissociation energies and are therefore a convenient computational tool for assessment of individual bond strength in polyatomic molecules. For nonspecific nonbonding interactions, the two-atom energies are low. They can be either repulsive or slightly attractive, but the DFT results more frequently yield small attractive values compared to the Hartree-Fock case. The hydrogen bond in the water dimer is calculated to be between the strong covalent and nonbonding interactions on the energy scale. 相似文献
65.
Zlatopolskiy BD Loscha K Alvermann P Kozhushkov SI Nikolaev SV Zeeck A de Meijere A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(19):4708-4717
The complete absolute configuration of hormaomycin 1 a has been established by HPLC and HPLC/MS experiments with appropriately derivatized 4-propylprolines, (2S,4S)-6 and (2R,4R)-6, as well as 4-(Z)-propenylprolines, cis-5 and trans-5, and also feeding experiments with enantiomerically pure samples of the deuterium-labeled 3-(2'-nitrocyclopropyl)alanine, (2S)-3,3-[D2]15 and (2S)-2,2'-[D2]15, and 4-(Z)-propenylproline 2',4-[D2]-(2S,4R)-5. The latter five amino acids were prepared for the first time and allowed one to unequivocally assign the hitherto unknown absolute configurations of the last four stereocenters in hormaomycin 1 a. As a bonus, some new information about the biosynthesis of this molecule has also been gathered. 相似文献
66.
A. I. Voloshin G. L. Sharipov V. P. Kazakov G. A. Tolstikov 《Russian Chemical Bulletin》1991,40(6):1158-1162
We have investigated chemiluminescence activated by Ru(bpy)3Cl2 in the reaction of decomposition of 1,2-dioxetane. Catalysis and activation of chemiluminescence of 1,2-dioxetanes by a ruthenium complex occur according to a mechanism of chemically initiated electron exchange, which leads to effective excitation of Ru(bpy)3Cl2 with yield
=0.20±0.05.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1316–1321, June, 1991. 相似文献
67.
68.
69.
A fast centroid molecular dynamics (CMD) methodology is proposed in which the effective centroid forces are predetermined through a force-matching algorithm applied to a standard path integral molecular dynamics simulation. The resulting method greatly reduces the computational cost of generating centroid trajectories, thus extending the applicability of CMD. The method is applied to the study of liquid para-hydrogen at two state points and liquid ortho-deuterium at one state point. The static and dynamical results are compared to those obtained from full adiabatic CMD simulations and found to be in excellent agreement for all three systems; the transport properties are also compared to experiment and found to have a similar level of agreement. 相似文献
70.
The splitting of the second maximum of the radial distribution function of an irregular atomic packing is regarded as an indication
of the amorphous state of a substance. This paper describes the splitting-forming atomic configurations using Delaunay simplices,
representing chains of elementary configurations. It is shown that the splitting is formed of chains in which all simplices
are nearly regular tetrahedra and quartoctahedra.
Translated fromZhumal Struktumoi Khimii, Vol. 38, No. 1, pp. 78–88, January–February, 1997. 相似文献