全文获取类型
收费全文 | 2207篇 |
免费 | 72篇 |
国内免费 | 10篇 |
专业分类
化学 | 1623篇 |
晶体学 | 10篇 |
力学 | 38篇 |
数学 | 351篇 |
物理学 | 267篇 |
出版年
2023年 | 7篇 |
2022年 | 20篇 |
2021年 | 46篇 |
2020年 | 44篇 |
2019年 | 45篇 |
2018年 | 33篇 |
2017年 | 34篇 |
2016年 | 62篇 |
2015年 | 46篇 |
2014年 | 69篇 |
2013年 | 104篇 |
2012年 | 135篇 |
2011年 | 187篇 |
2010年 | 88篇 |
2009年 | 89篇 |
2008年 | 145篇 |
2007年 | 138篇 |
2006年 | 125篇 |
2005年 | 121篇 |
2004年 | 109篇 |
2003年 | 102篇 |
2002年 | 93篇 |
2001年 | 38篇 |
2000年 | 42篇 |
1999年 | 31篇 |
1998年 | 25篇 |
1997年 | 15篇 |
1996年 | 28篇 |
1995年 | 14篇 |
1994年 | 13篇 |
1993年 | 25篇 |
1992年 | 19篇 |
1991年 | 11篇 |
1990年 | 13篇 |
1989年 | 12篇 |
1988年 | 9篇 |
1987年 | 14篇 |
1986年 | 12篇 |
1985年 | 9篇 |
1984年 | 12篇 |
1983年 | 4篇 |
1982年 | 15篇 |
1981年 | 10篇 |
1980年 | 9篇 |
1979年 | 7篇 |
1978年 | 9篇 |
1977年 | 11篇 |
1976年 | 12篇 |
1975年 | 9篇 |
1974年 | 6篇 |
排序方式: 共有2289条查询结果,搜索用时 31 毫秒
981.
Very often only “diagonal” second order energies, varying as an even power of R?1, occur in the multipole expansion of the interaction energy. However for many molecular interactions important “nondiagonal” second order energies, varying as an odd or even power of R?1 can arise. This point is emphasized by a general discussion and by a detailed specific example, the interaction of an ionized dipolar molecule with a nondegenerate atom. Also some useful theorems, on the orientation average of various types of second order energies, are derived. 相似文献
982.
The nature of the excited states of [Ru(bpy)2dppz]2+ has been investigated using density functional theory with the hybrid functional B3LYP. The excitations were studied via linear response theory (TDDFT) and DeltaSCF calculations and the solvent effects were introduced by embedding the molecule in a continuum dielectric medium. It was found that the solvent effects are critical in understanding the nature of the excitations. For the molecule in ethanol, the lowest absorption predicted by TDDFT is a dark state 3pi --> pi with the electron and hole spread over the dppz ligand. Next come the excitations of 3MLCT between the ruthenium and the dppz and finally the 3MLCT excitations between the ruthenium and the bpy ligands not associated with the phenazine. Using deltaSCF calculations two low-lying excited states were identified and the geometry optimized in the presence of the continuum medium. At the optimal geometry the lowest excited state is 3MLCT (Ru --> dppz). The 3pi --> pi state is found only 0.026 eV higher. 相似文献
983.
Casado J Miller LL Mann KR Pappenfus TM Higuchi H Ortí E Milián B Pou-Amérigo R Hernández V López Navarrete JT 《Journal of the American Chemical Society》2002,124(41):12380-12388
Two quinonoid bis(dicyanomethylene) oligothiophenes, terthiophene and quaterthiophene analogues of TCNQ, have been investigated by spectroelectrochemical experiments and density functional theory calculations. Electrochemical data show that the molecules can be both reduced and oxidized at relatively low potentials, and that the quaterthiophene derivative forms four stable redox species, the dianion, neutral, cation radical, and dication. The neutral oligomers are characterized by a strong electronic absorption in the red or near-infrared region and can be viewed as structural and electronic analogues of aromatic oligothiophenes in the dication or bipolaron state. Upon reduction, dianions, not anion radicals, are formed which absorb in the visible region. The theoretical calculations show that the dianions have aromatic oligothiophene moieties with two anionic dicyanomethylene groups. The transition from a quinonoid to an aromatic structure is fully supported by UV-vis-near-IR and vibrational spectroscopic data. Oxidation, generating cation radicals and dications, occurs at rather low potentials similar to those reported for oligothiophenes. The electronic spectra of these cations are understood from the calculations, which suggest that the oxidized species are stabilized by the partial aromatization of the oligothiophene backbone. IR spectra of the species, especially the CN stretching frequencies, confirm the structural conclusions and allow comparison with TCNQ and the TCNQ dianion. 相似文献
984.
L. F. Errea A. Macías L. Mndez A. Riera B. Pons I. Sevila 《International journal of quantum chemistry》2002,86(1):46-58
Molecular orbitals are presented in configuration and momentum representations. We propose to minimize large oscillations present in calculated momentum wavefunctions by cancelling position factor phases. We illustrate the distortion introduced by different electron translation factors and show continuum states and dynamical wavefunctions in momentum coordinates. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001 相似文献
985.
Verdaguer X Lledó A López-Mosquera C Maestro MA Pericàs MA Riera A 《The Journal of organic chemistry》2004,69(23):8053-8061
Here we describe the synthesis and use of the Pulegone-derived bidentate P,S ligands PuPHOS and CyPuPHOS in the intermolecular Pauson-Khand reaction. Ligand exchange reaction of hexacarbonyldicobalt-alkyne complexes with PuPHOS provides a diasteromeric mixture of complexes (up to 4.5:1) from which the major isomers can be conveniently separated by simple crystallization. An isomerization-crystallization sequence of the original mixture results in a dynamic resolution that allows the preparation of the pure major Co(2)(mu-TMSC(2)H)(CO)(4)-PuPHOS (15a) in a multigram scale. Pauson-Khand reaction of 15a with norbornadiene provided, for the first time, the corresponding enone 18 with up to 93% yield and 97% ee. The use of (+)-18 as a surrogate of chiral cyclopentadienone is also demonstrated. Copper-catalyzed Michael addition of a Grignard reagent followed by removal of the TMS group with TBAF were the most reliable methods to transform (+)-18 into valuable starting materials 20a-e for the enantioselective synthesis of cyclopentenoid systems. 相似文献
986.
Mirenda M Lagorio MG San Román E 《Langmuir : the ACS journal of surfaces and colloids》2004,20(9):3690-3697
A method for the calculation of absolute fluorescence quantum yields for dyes attached to solid particles based on reflectance measurements is reported. The same procedure allows calculation of true reflectance spectra (free of fluorescence) for highly fluorescent materials as well. Samples ofcresyl violet were immobilized by adsorption on microgranular cellulose in the concentration range 4.5 x 10(-9) to 3.8 x 10(-6) mol g(-1). Diffuse and total reflectance spectra were recorded with and without insertion of an optical absorption filter between the output of the integrating sphere of a reflectance spectrometer and the photodetector in order to block fluorescence partially. From these data, the relative emission spectrum of the dye, the filter transmission spectrum, and the detector sensitivity, true reflectances and absolute fluorescence quantum yields were recovered. Observed fluorescence quantum yields, affected by dye aggregation and inner filter effects, were concentration and wavelength dependent, ranging approximately between 0.1 and 0.6. The analysis of remission function spectra showed that dye aggregation is negligible up to a concentration of 1.41 x 10(-7) mol g(-1). Fluorescence data were corrected for reemission and reabsorption using a suitable model [Lagorio, M. G.; Dicelio, L. E.; Litter, M. I.; San Roman, E. J. Chem. Soc., Faraday Trans. 1998, 94, 419]. Application of this model to samples showing no aggregation yielded a wavelength-independent true fluorescence quantum yield of 0.60 +/- 0.05, similar to values found in solution. The usage of cresyl violet as a reference for the evaluation of fluorescence quantum yields for weakly fluorescing samples in the solid phase is discussed. 相似文献
987.
Enrique Cadenas Helmut Siesi Ana Campa Giuseppe Cilento 《Photochemistry and photobiology》1984,40(5):661-666
Abstract —Chlorophyll- a enhances the photoemission from the microsomeltert-butyl hydroperoxide system without affecting the rates of O2 uptake and lipid peroxidation. This photoemission, due to energy transfer from triplet carbonyls to microsome-bound chlorophyll- a , shows that microsomal membranes produce a significant amount of excited triplet carbonyls during lipid peroxidation. 相似文献
988.
Errea LF Fernández L Macías A Méndez L Rabadán I Riera A 《The Journal of chemical physics》2004,121(4):1663-1669
We present a method to ensure the sign consistency of dynamical couplings between ab initio three-center wave functions. The method also allows to systematically "diabatize" avoided crossings between two potential energy surfaces, including conical intersections. Illustrations are presented for H(3)(+), LiH(2)(+), and NH(2)(5+) quasimolecules. 相似文献
989.
Castro EA Cubillos M Aliaga M Evangelisti S Santos JG 《The Journal of organic chemistry》2004,69(7):2411-2416
The reactions of a series of secondary alicyclic (SA) amines with O-phenyl and O-ethyl O-(2,4-dinitrophenyl) thiocarbonates (1 and 2, respectively) and of a series of pyridines with the former substrate are subjected to a kinetic investigation in water, at 25.0 degrees C, ionic strength 0.2 M (KCl). Under amine excess over the substrate, all the reactions obey pseudo-first-order kinetics and are first-order in amine. The Br?nsted-type plots are biphasic, with slopes (at high pK(a)) of beta(1) = 0.20 for the reactions of SA amines with 1 and 2 and beta(1) = 0.10 for the pyridinolysis of 1 and with slopes (at low pK(a)) of beta(2) = 0.80 for the reactions of SA amines with 1 and 2 and beta(2) = 1.0 for the pyridinolysis of 1. The pK(a) values at the curvature center (pK(a)(0)) are 7.7, 7.0, and 7.0, respectively. These results are consistent with the existence of a zwitterionic tetrahedral intermediate (T++) and a change in the rate-determining step with the variation of amine basicity. The larger pK(a)(0) value for the pyridinolysis of 1 compared to that for 2 (pK(a)(0) = 6.8) and the larger pK(a)(0) value for the reactions of SA amines with 1 relative to 2 are explained by the greater inductive electron withdrawal of PhO compared to EtO. The larger pK(a)(0) values for the reactions of SA amines with 1 and 2, relative to their corresponding pyridinolysis, are attributed to the greater nucleofugalities of SA amines compared to isobasic pyridines. The smaller pK(a)(0) value for the reactions of SA amines with 2 than with O-ethyl S-(2,4-dinitrophenyl) dithiocarbonate (pK(a)(0) = 9.2) is explained by the greater nucleofugality from T(++) of 2,4-dinitrophenoxide (DNPO(-)) relative to the thio derivative. The stepwise reactions of SA amines with 1 and 2, in contrast to the concerted mechanisms for the reactions of the same amines with the corresponding carbonates, is attributed to stabilization of T(++) by the change of O(-) to S(-). The simple mechanism for the SA aminolysis of 2 (only one tetrahedral intermediate, T(++)) is in contrast to the more complex mechanism (two tetrahedral intermediates, T(++) and T(-), the latter formed by deprotonation of T(++) by the amine) for the same aminolysis of the analogous thionocarbonate with 4-nitrophenoxide (NPO(-)) as nucleofuge. To our knowledge, this is the first example of a remarkable change in the decomposition path of a tetrahedral intermediate T by replacement of NPO(-) with DNPO(-) as the leaving group of the substrate. This is explained by (i) the greater leaving ability from T(++) of DNPO(-) than NPO(-) and (ii) the similar rates of deprotonation of both T(++) (formed with DNPO and NPO). 相似文献
990.
Reactions of 4-methylphenyl 4-nitrophenyl carbonate (MPNPC) and 4-chlorophenyl 4-nitrophenyl carbonate (ClPNPC) with a series of quinuclidines (QUIN) and the latter carbonate with a series of secondary alicyclic amines (SAA) are subjected to a kinetic investigation in 44 wt % ethanol-water, at 25.0 degrees C and an ionic strength of 0.2 M. The reactions were followed spectrophotometrically at 330 or 400 nm (4-nitrophenol or 4-nitrophenoxide anion appearance, respectively). Under excess amine, pseudo-first-order rate coefficients (k(obsd)) are found. For all these reactions, plots of k(obsd) vs free amine concentration at constant pH are linear, the slope (k(N)) being independent of pH. The Br?nsted-type plots (log k(N) vs pK(a) of the conjugate acids of the amines) for the reactions of the series of QUIN with MPNPC and ClPNPC are linear with slopes (beta(N)) 0.88 and 0.87, respectively, which are explained by a stepwise process where breakdown of a zwitterionic tetrahedral intermediate (T(+/-)) to products is rate limiting. The Br?nsted-type plot for the reactions of the series of SAA with ClPNPC is biphasic with slopes beta(1) = 0.2 (high pK(a) region) and beta(2) = 0.9 (low pK(a) region) and a curvature center at pK(a)(0) = 10.6. This plot is in accordance with a stepwise mechanism through T(+/-) and a change in the rate-determining step, from T(+/-) breakdown to T(+/-) formation as the basicity of the SAA increases. Two conclusions arise from these results: (i) QUIN are better leaving groups from T(+/-) than isobasic SAA, and (ii) the non-leaving group effect on k(N) for these reactions is small, since beta(nlg) ranges from -0.2 to - 0.3. From these values, it is deduced that ClPNPC is ca. 70% more reactive than MPNPC toward SAA and QUIN, when expulsion of the leaving group from T(+/-) is the rate determining step. 相似文献